Antistatic film, spacer using it and picture display unit
Abstract
An antistatic film which has a structure that comprises a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
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Projected expiry passed 21 January 2025, 1.7 years ago.
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30 claims: 11 independent, 19 dependent
- 1An antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
- 2An antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
- 9An antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
- 10An antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
- 11An antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.
- 16A mixture target of aluminum and platinum including 95 wt.% or more aluminum and platinum, which is used for forming an antistatic film containing aluminum and platinum by a sputtering technique.
- 17A mixture target of aluminum nitride and platinum including 95 wt.% or more aluminum and platinum, which is used for forming an antistatic film containing aluminum and platinum by a sputtering technique.
- 21A mixture target of aluminum and gold including 95 wt.% or more aluminum and gold, which is used for forming an antistatic film containing aluminum and gold by a sputtering technique.
- 22A mixture target of aluminum nitride and gold including 95 wt.% or more aluminum and gold, which is used for forming an antistatic film containing aluminum and gold by a sputtering technique.
- 26A mixture target of aluminum and silver including 95 wt.% or more aluminum and silver, which is used for forming an antistatic film containing aluminum and silver by a sputtering technique.
- 27A mixture target of aluminum nitride and silver including 95 wt.% or more aluminum and silver, which is used for forming an antistatic film containing aluminum and silver by a sputtering technique.
Independent claims12
433 paragraphs in 4 sections, as filed
BACKGROUND OF THE INVENTION
Field of the Invention
0001The present invention relates to an antistatic film installed in an airtight vessel containing an electron source of an electron-generating device such as a picture display unit, to a spacer using it, and to the picture display unit.
Related Background Art
0002A flat display unit using an electron-emitting device has, as shown in Japanese Patent Application Laid-Open No. <patcit id="pcit0001" dnum="JPH10284286B"><text>H10-284286</text></patcit>, a spacer called as the spacer or a rib installed therein, which is a structural support resistant to ambient pressure for keeping the inside of the unit into a high vacuum.
0003<figref idref="f0006">FIG. 7</figref> is a cross-sectional schematic view of an image-forming apparatus using many electron-emitting devices. Reference numeral 101 denotes a rear plate, reference numeral 102 a sidewall and reference numeral 103 a faceplate, and an airtight vessel is formed by the rear plate 101, the side wall 102 and the face plate 103. A spacer 107b that is a structural support resistant to ambient pressure in the airtight vessel has a low-resistivity film 110 thereon, and is connected to wiring 109 through an electroconductive frit 108.
0004An electron-emitting device 104 is formed on a rear plate 101, and a phosphor 105 and a metal back 106 are formed on a face plate. Objects of providing a metal back 106 are to improve a utilization factor of light by mirror-reflecting a light emitted from a phosphor 105; to protect the phosphor 105 from the collision of negative ions; to work as an electrode for applying an electron beam-accelerating voltage; and to work as a conducting path for electrons after having excited the phosphor 105.
0005A spacer 107a shows the electrostatically charged state of the spacer, and shows a state in which electrostatic charge (positive electrostatic charge in the drawing) is caused by collision of one part of electrons emitted from an electron source around it. Here, the spacer 107a shows the electrostatically charged state of the spacer when having no antistatic film 112 installed thereon, and thus, the thickness of a low-resistivity film is drawn more thickly than the low-resistivity film 110 contacting with the antistatic film 112 of the spacer 107b, for convenience in illustration.
0006When a spacer 107a is positively charged with electricity as described above, electrons emitted from an electron-emitting device 104 that is an electron source are drawn to a spacer side, for example, like an electron trajectory 111a, and consequently impair the quality of a displayed image.
0007In order to solve the problem, there is a proposition of arranging an antistatic film 112 on a spacer 107b, eliminating the charge by passing a micro electrical current through the surface, and thereby making electrons draw a predetermined trajectory such as an electron trajectory 111b, without being drawn to the spacer. There is also a proposition, as shown in Japanese Patent Application Laid-Open No. <patcit id="pcit0002" dnum="JP2001143620A"><text>2001-143620</text></patcit>, of providing unevenness on the surface of a spacer glass substrate to make an effective secondary emission coefficient less than that with a flat spacer surface, and to effectively inhibit the electrostatic charge of the spacer surface.
0008Furthermore, Japanese Patent Application Laid-Open No. <patcit id="pcit0003" dnum="JPH10284283B"><text>H10-284283</text></patcit> proposes a spacer coated with an electrostatic charge-mitigating film containing aluminum nitride or aluminum oxide, and noble metals such as gold, palladium and platinum, by binary simultaneous sputtering with the use of an aluminum target and a noble metal target, and of a mixed gas of argon and nitrogen or oxygen as a gas for forming a film.
0009However, it has become clear that the spacers shown in the above described conventional examples cause variation in the performance of the function for eliminating electrostatic charge.
0010In particular, when a temperature distribution is formed in the spacer, the distribution of resistivity is also formed due to the temperature characteristic of the resistivity of the antistatic film. The variation of resistivity leads to the variation in the diselectrification function.
0011Specifically, in a flat display panel, the instability of a display image results from temperature distribution in a panel plane, which is caused by a temperature difference between a face plate and a rear plate.
0012In addition, a conventional method of forming an antistatic film containing a plurality of elements by sputtering simultaneously a plurality of different material targets (for example, binary sputtering with the use of two materials) might cause variation in the resistivity of an antistatic film depending on each film-forming batch even when film-forming conditions (background, sputtering pressure, gas flow rate and target electrification power) are uniformized.
0013In order to uniformize resistivity, target electrification powers supplied to different material targets are required to be adjusted to each, which is complicated, and the operation is not always highly reproducible. In particular, in binary sputtering, when there is a large difference between target electrification powers, so-called cross contamination can not be avoided, which is a phenomenon that a more powerfully electrified target material deposits on the surface of a less powerfully electrified target material.
SUMMARY OF THE INVENTION
0014An object of the present invention is to provide an antistatic film having superior controllability for a resistivity value,'stability and reproducibility, and the adequate temperature characteristics of resistance.
0015The present invention provides an antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
0016In addition, the present invention provides an antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
0017In addition, the present invention provides an antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.
0018In addition, the present invention provides an antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
0019In addition, the present invention provides an antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
0020In addition, the present invention provides an antistatic film having a structure of dispersing a plurality of semiconductive particles with particle diameters of 0.5 to 10 nm in a medium containing a nitride and an oxide. As for media,which it was described above, it points at the part except for the particles which have the particle diameters of 0.5 to 10nm dispersed in a film and which exists.
0021In addition, the present invention provides an electron-generating device with an electron source in an airtight vessel, comprising any of the above described antistatic films in the airtight vessel.
0022In addition, the present invention provides a picture display unit provided with an airtight vessel having a first substrate with an electron source arranged thereon, and a second substrate with an image display member arranged thereon so as to face the electron source, and a spacer arranged between the first and second substrates in the above described airtight vessel, wherein the spacer has any of the above described antistatic films arranged on the surface.
0023In addition, the present invention provides a spacer arranged between a first substrate and a second substrate in a picture display unit provided with an airtight vessel having the first substrate with an electron source arranged thereon and the second substrate having an image display member arranged thereon so as to face the electron source, wherein the spacer has any of the above described antistatic films on the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
0024<ul id="ul0001" list-style="none" compact="compact"><li><figref idref="f0001">FIG. 1</figref> is a schematic view showing the cross-sectional shape of an antistatic film according to the present invention, observed with a TEM (a transmission electron microscope);</li><li><figref idref="f0002">FIG. 2</figref> is a perspective view showing a picture display unit according to the present invention, of which one part of the display panel is cut;</li><li><figref idref="f0003">FIG. 3</figref> is a block diagram of a high-frequency sputtering apparatus arranging a target according to the present invention therein, which is used for imparting an antistatic film to a spacer substrate;</li><li><figref idref="f0004">FIG. 4</figref> is a figure showing a relation between the resistivity of a Pt-Al mixture-nitride film according to the present invention and the total pressure of a sputtering gas;</li><li><figref idref="f0004">FIG. 5</figref> is a figure showing a relation between the resistivity of a Pt-AlN mixture-nitride film according to the present invention and the total pressure of a sputtering gas;</li><li><figref idref="f0005">FIG. 6</figref> is a figure showing the variation of the resistivity of a Pt-Al mixture-nitride film according to the present invention;</li><li><figref idref="f0006">FIG. 7</figref> is a cross-sectional schematic view of an image-forming apparatus using an electron-emitting device, for describing the mechanism of an electrostatic charge in a spacer according to the present invention; and</li><li><figref idref="f0006">FIG. 8</figref> is a view explaining the deviation of an electron beam ΔL which appears as the disarray of a display image due to the influence of a spacer according to the present invention.</li></ul>
DESCRIPTION OF THE PREFERRED EMBODIMENTS
0025The present invention provides an antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
0026In addition, the present invention provides an antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
0027In addition, the present invention provides an antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.
0028In addition, the conductor particle is preferably a noble metal particle.
0029In addition, the conductor particle is preferably a platinum particle, and the nitride is preferably aluminum nitride.
0030In addition, the conductor particle is preferably a platinum particle, and the oxide is preferably aluminum oxide.
0031In addition, the conductor particle is preferably a platinum particle, a nitride is preferably aluminum nitride, and the oxide is preferably aluminum oxide.
0032In addition, the conductor particle is preferably a gold particle, and the nitride is preferably aluminum nitride.
0033In addition, the conductive particle is preferably a gold particle, and the oxide is preferably aluminum oxide.
0034In addition, the conductor particle is preferably a gold particle, the nitride is preferably aluminum nitride, and the oxide is preferably aluminum oxide.
0035In addition, the conductor particle is preferably a silver particle, and the nitride is preferably aluminum nitride.
0036In addition, the conductor particle is preferably a silver particle, and the oxide is preferably aluminum oxide.
0037In addition, the conductor particle is preferably a silver particle, the nitride is preferably aluminum nitride, and the oxide is preferably aluminum oxide.
0038In addition, the content of the conductor is preferably 0.1 to 10 atomic%.
0039In addition, the present invention provides an antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
0040In addition, the present invention provides an antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
0041In addition, the present invention provides an antistatic film having a structure of dispersing a plurality of semiconductive particles with particle diameters of 0.5 to 10 nm in a medium containing a nitride and an oxide.
0042In addition, the semiconductor particle is preferably a germanium particle, and the nitride is preferably silicon nitride.
0043In addition, the semiconductor particle is preferably a germanium particle, and the oxide is preferably silicon oxide.
0044In addition, the conductor particle is preferably a germanium particle, the nitride is preferably silicon nitride, and the oxide is preferably silicon oxide.
0045In addition, the content of the semiconductor is preferably 0.1 to 10 atomic%.
0046In addition, any of the above described antistatic films includes the particle with a diameter of 1.0 to 9.0 nm, and has a resistivity of p = 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm.
0047In addition, the present invention provides an electron-generating device with an electron source in an airtight vessel, comprising any of the above described antistatic films in the airtight vessel.
0048In addition, the present invention provides a picture display unit provided with an airtight vessel having a first substrate with an electron source arranged thereon, and a second substrate with an image display member arranged thereon so as to face the electron source, and a spacer arranged between the first and second substrates in the above described airtight vessel, wherein the spacer has any of the above described antistatic films arranged on the surface.
0049In addition, the present invention provides a spacer arranged between a first substrate and a second substrate in a picture display unit provided with an airtight vessel having the first substrate with an electron source arranged thereon and the second substrate having an image display member arranged thereon so as to face the electron source, wherein the spacer has any of the above described antistatic films on the surface.
0050The above described antistatic film according to the present invention has little change of resistivity due to temperature, and when the antistatic film is provided particularly on the surface of the spacer of the picture display unit, it has the effect of reducing the instability of a display image, which originates from a temperature distribution in an airtight vessel caused by a temperature difference between the above described first and second substrates.
0051Furthermore, the present invention provides a mixture target of aluminum and platinum including 95 wt.% or more aluminum and platinum, which is used for forming an antistatic film containing aluminum and platinum by a sputtering technique.
0052In addition, the present invention provides a mixture target of aluminum nitride and platinum including 95 wt.% or more aluminum and platinum, which is used for forming an antistatic film containing aluminum and platinum by a sputtering technique.
0053Furthermore, the present invention provides a method for manufacturing an antistatic film containing aluminum and platinum, comprising sputtering the mixture target in an atmosphere containing only nitrogen.
0054In addition, the present invention provides a method for manufacturing an antistatic film containing aluminum and platinum, comprising sputtering the mixture target in an atmosphere containing only oxygen.
0055In addition, the present invention provides a method for manufacturing an antistatic film containing aluminum and platinum, comprising sputtering the mixture target in an atmosphere containing nitrogen and oxygen.
0056A target according to the present invention, as described above, can be preferably used as a target particularly of a PVD (Physical Vapor Deposition) apparatus such as an electron beam evaporation apparatus and a sputtering apparatus. When the PVD (Physical Vapor Deposition) apparatus employs a target according to the present invention as the target thereof, it can produce a resistive film having high reproducibility, superior controllability of a resistivity value, and temperature characteristics of the resistance.
0057In addition, a method for manufacturing an antistatic film according to the present invention has the effect comprising the variation of the resistivity less and the reproducibility of the film characteristic (resistivity) higher than those with binary simultaneous sputtering.
(Embodiments)
0058First of all, an antistatic film according to the present invention is a resistive film as shown in <figref idref="f0001">FIG. 1</figref> that is a schematic view showing the cross-sectional shape observed with a TEM (a transmission electron microscope), having a structure comprising a plurality of particles 1 with an average particle diameter of 0.5 to 10 nm dispersed in a medium 2. Here, the average particle diameter is obtained by measuring the diameters of 20 particles in a cross-sectional shape as shown in <figref idref="f0001">FIG. 1</figref> and calculating the average.
0059If the particles have an average particle diameter of 0.5 nm or larger, preferably 1 nm or larger, a resistive film including them can be judged to have adequate temperature characteristics of resistance. Specifically, the resistive film can be judged to have little variation of resistance due to a temperature change. Accordingly, when the spacer having the resistive film as an antistatic film is used in a picture display unit, the spacer can reduce the disarray of a display image caused by it. In addition, the above described average particle diameter is 10 nm or smaller, and preferably 9 nm or smaller from the viewpoint comprising a resistivity of the resistive film equal to or higher than 1×10<sup>6</sup> Ωcm.
0060As described above, the above described resistive film contains an electron source, is arranged in an airtight vessel having temperature change, and is preferably applied to the resistive film for preventing electrostatic charge in the airtight vessel, namely, to an antistatic film.
0061Embodiments according to the present invention will be now described below.
0062At first, a first embodiment shows a resistive film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
0063A second embodiment shows a resistive film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
0064A third embodiment shows a resistive film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.
0065In each embodiment described above, the conductor is preferably a metal such as platinum, gold, silver, and among the metals, particularly preferably is platinum or gold from the viewpoint of stability and controllability for a resistivity value. In addition, the above described nitride is preferably aluminum nitride, germanium nitride, silicon nitride and magnesium nitride, and among them, particularly preferably is aluminum nitride from the viewpoint of stability and controllability for a resistivity value. In addition, the above described oxide is preferably aluminum oxide, germanium oxide, silicon oxide and magnesium oxide, and among them, particularly preferably is aluminum oxide from the viewpoint of stability and controllability for a resistivity value. In addition, the above described medium containing a nitride and an oxide, particularly preferably is aluminum nitride/oxide from the viewpoint of stability and controllability for a resistivity value, and the adequate temperature characteristics of resistance.
0066Subsequently, a fourth embodiment shows a resistive film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.
0067A fifth embodiment shows a resistive film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.
0068The sixth embodiment shows a resistive film having a structure comprising a plurality of semiconductive particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.
0069In the fourth, fifth and sixth embodiments described above, the above semiconductor is preferably germanium, silicon and the like, and among the semiconductors, is particularly preferably germanium from the viewpoint of stability and controllability for a resistivity value. In addition, the above described nitride is preferably aluminum nitride, germanium nitride, silicon nitride and magnesium nitride, and among them, particularly preferably is silicon nitride from the viewpoint of stability and controllability for a resistivity value. In addition, the above described oxide is preferably aluminum oxide, germanium oxide, silicon oxide and magnesium oxide, and among them, particularly preferably is silicon oxide from the viewpoint of stability and controllability for a resistivity value. In addition, the above described medium containing a nitride and an oxide, particularly preferably is silicon nitride/oxide from the viewpoint of stability and controllability for a resistivity value, and the adequate temperature characteristics of resistance.
0070In addition, when the resistive film of each of above described first to sixth embodiments is applied to an antistatic film on the surface of a spacer arranged between first and second substrates particularly of a picture display unit provided with an airtight vessel having the first substrate with an electron source arranged thereon and the second substrate with an image display member arranged so as to face the above described electron source, among electron-generating devices, the above each resistive film has the resistivity preferably of p = 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm, and has a conductor or semiconductor content preferably of 0.1 to 10 atomic%.
0071Subsequently, a method for obtaining the above described resistive film will be described.
0072The above described resistive film is preferably formed (1) with a sputtering technique by using a mixture target containing at least a component composing a conductor particle or a semiconductor particle and a component to be nitrided or oxidized for composing a nitride or an oxide, and (2) in a sputtering atmosphere containing nitrogen gas with a nitrogen partial pressure of 70% or higher, or oxygen gas with an oxygen partial pressure of 70% or higher. As a matter of course, the atmosphere may be a mixed gas atmosphere if the partial pressure is in the above described range. In addition, the mixed gas atmosphere is particularly preferably the atmosphere of the gas of nitrogen mixed with oxygen, and in this case, the partial pressure of nitrogen and oxygen is preferably controlled to 70% or more in total.
0073The particle diameter can be appropriately varied in the range of 0.5 to 10 nm by changing the component and the ratio in the composition of a mixing target, and a gas sort, a sputtering pressure and an electrification power during film formation by sputtering, in the above described conditions (1) and (2), so that a resistive film can be obtained so as to acquire the resistance controlled to a preferable range for an electron generating device to which the resistive film is applied.
0074Subsequently, a sputtering apparatus used for forming the resistive film according to the above described embodiments will be described.
(Sputtering apparatus)
0075<figref idref="f0003">FIG. 3</figref> shows the configuration of a high-frequency sputtering apparatus used in the present embodiment.
0076The summary of the process of forming the above described resistive film by using it will be now described. At first, a substrate 201 is put on a film-forming tray 202, and is charged into a preliminary exhaust hood 203. The preliminary exhaust hood is exhausted to a vacuum degree of 5x10<sup>-4</sup> [Pa] or lower with a vacuum pump 204, and then the film-forming tray 202 is moved to a film-forming chamber 206 by a conveyance roller 205. Then, the film-forming chamber 206 is evacuated to a vacuum of 2×10<sup>-5</sup> [Pa] or less. After the vacuum has been confirmed to have reached the above described value, the specified quantity of a nitrogen gas, an oxygen gas, the mixed gas of argon and nitrogen, the mixed gas of argon and oxygen, or the mixed gas of nitrogen and oxygen is passed into the film-forming chamber through a gas introduction pipe 207. An orifice (not shown) is adjusted so that the total pressure of a sputtering gas becomes a predetermined pressure. After an atmosphere (the total pressure of a sputtering gas, a gas flow rate) has become stable, a predetermined power is applied to a high-frequency power source 208. In order to form a resistive film all over the surface of a substrate 201, a film-forming tray 202 is transported by a transporting roller 205 at the rate of 5 mm/min in the direction of an arrow in the drawing so as to cross directly under.a mixture target 209, after sputtering discharge has started. The distance between the substrate and the mixture target is set to 200 mm.
0077Here, the high voltage of direct current applied to the mixture target 209 is adjusted by a high-frequency power source 208 so that the variation originating from the transportation of the substrate can be reduced.
0078The direction of transporting the substrate is not limited to one direction, but one-return transportation or a plurality of return transportation is acceptable. In addition, in some configurations of the apparatus, a film may be formed on the whole surface by rotating the substrate directly under the target.
0079Through the above described steps, a resistive film can be formed on a substrate.
0080In addition, when a resistive film is to be formed on both sides of a substrate, the film is formed on a surface (a first surface), then a film-forming tray 202 is returned to a preliminary exhaust hood 203, and the substrate 201 is taken out. Subsequently, the substrate 201 is reversed, and the above described resistive film is formed on a back surface (a second surface) similarly to the top surface (the first surface).
0081The resistive film to be formed on each surface of the top surface (a first surface) and the back surface (a second surface) may be a single-layered film with a desired film thickness, or a multilayer film consisting of a plurality of layers, which is produced by using a plurality of targets each having a different composition concentration ratio of the mixture from others.
0082Subsequently, a mixture target used in the above described sputtering apparatus will be described.
(Method for producing mixture target)
0083Here, a method for producing the above described mixture-sintered target will be described.
1) Mixing
0084At first, the weight of each powder of the above described components is measured in accordance with various composition concentration ratios, and the powders are mixed. For instance, the powders of Pt and Al, or Pt and AlN are mixed. A mixing device is not limited in particular, but a ball mill may be used. The powders are mixed in a non-oxidative atmosphere of nitrogen gas, Ar gas or the like. After the powders have been mixed, they may be classified by a sieve or the like as needed.
2) Calcination
0085The mixed powder is calcined in an inert atmosphere of nitrogen gas, Ar gas or the like, or in a vacuum. Alternatively, it may be calcined in a reducing atmosphere of hydrogen or the like. The mixed powder is preferably heated to 800 to 1,500°C, for calcination.
3) Pulverization
0086Thus formed solid material is pulverized. A pulverizing device is not limited in particular, but a ball mill may be used. The solid material is pulverized in a non-oxidative atmosphere of nitrogen gas, Ar gas or the like. After the solid material has been pulverized, the product may be classified with a sieve or the like as needed.
4) Baking
0087The mixed powder obtained through pulverization is pressure-baked in an inert atmosphere of nitrogen gas, Ar gas or the like, or in a vacuum, and a sintered compact is thereby obtained. The mixed powder may be pressure-baked in a reducing gas atmosphere of hydrogen or the like. Hot pressing is preferably used for pressure baking. The sintered compact is formed so as to have a predetermined plate thickness and shape for being sputtered, then is preferably heated to 800 to 1,500°C under the pressure of 1 to 2 MPa, which is a baking step, and becomes a mixture-sintered target.
(Method for producing mixture-melted alloy target)
0088Here, a method for producing a mixture-melted alloy target will be described.
1) Melting
0089At first, the weight of each raw material of the above described components is measured in accordance with various composition concentration ratios, and the raw materials are mixed. For instance, the raw materials of Pt and Al, or Pt and AlN are mixed, and melt in a melting furnace. A melting method for the raw materials is not limited in particular, but in order to prevent the contamination of atmospheric impurities, the raw materials are desirably melt in a vacuum.
2) Cooling
0090The above described melted mixture is cooled while the condition is adjusted not so as to cause the segregation of components.
3) Forge-rolling
0091Thus produced solid material is forge-rolled while being heated. A void (a cavity) produced during cooling is filled, and melting irregularity and density irregularity are uniformized.
4) Baking
0092The solid material obtained through the above described steps is pressure-baked in an inert atmosphere of Ar gas or the like, or in a vacuum, and a Pt-Al or Pt-AlN mixture-melting alloy is thereby obtained. The solid material may be pressure-baked in a reducing gas atmosphere of hydrogen or the like. Hot pressing is preferably used for pressure baking. The mixture-melting alloy is formed so as to have a predetermined plate thickness and shape for being, sputtered, and becomes a mixture-melted alloy target.
0093In the same way as described above, an aluminum-platinum mixture target containing 95 wt.% or more aluminum and platinum, or an aluminum nitride -platinum mixture target containing 95 wt.% or more aluminum and platinum can be formed.
0094In the next place, the whole configuration of a picture display unit will be described, in which a substrate having the above described resistive film formed thereon as a spacer, and the spacer is inserted into the picture display unit.
(Panel configuration)
0095<figref idref="f0002">FIG. 2</figref> is a perspective view of a display panel in a picture display unit according to the present embodiment, in which one part of the panel is cut in order to show an inner structure.
0096In the figure, reference numeral 915 denotes a rear plate, reference numeral 916 a side wall, and reference numeral 917 a face plate. The rear plate 915, the side wall 916 and the face plate 917 forms an airtight vessel for keeping the inside of the display panel into a vacuum. When the airtight vessel is assembled, joining areas between members need to be sealed in order to make the joining areas retain adequate strength and airtightness. The sealing is achieved, for example, by applying frit glass to the joining areas and baking it at 400 to 500°C for 10 minutes or longer in atmospheric air or a nitrogenous atmosphere. A method for evacuating the inside of an airtight vessel to a vacuum will be described later.
0097In addition, the inside of the above described airtight vessel is kept in a vacuum of about 10<sup>-4</sup> [Pa], so that for the purpose of preventing the destruction of the airtight vessel due to an ambient pressure or unexpected shock, a spacer 920 is provided so as to make the airtight vessel an ambient-pressure resistant structure. As the spacer, a substrate having an antistatic film is used, which is produced by using the above described mixture targets having various composition concentration ratios in forming films.
0098A substrate 911 is fixed on a rear plate 915, while having N×M pieces of surface conduction electron-emitting devices 912 formed thereon. Here, N and M are positive integers of 2 or more and are appropriately set in accordance with an objective display pixel number. For instance, in a display device for displaying a high definition picture, those numbers are preferably N = 3,000 and M = 1,000 or more. In the present embodiment, the numbers are set to N = 3,072 and M = 1,024.
0099The above described N×M pieces of surface conduction electron-emitting devices are simple-matrix-wired by M lines of row-directional wiring 913 and N lines of column-directional wiring 914. The part composed by the substrate 911, the surface conduction electron-emitting devices 912, the row-directional wiring 913 and the column-directional wiring 914 is called an electron source substrate.
0100In addition, a fluorescent screen 918 is formed on the undersurface of a faceplate 917. In addition, a metal back 919, which is well known in the field of CRT, is arranged on the surface of the rear plate side of the fluorescent screen 918.
0101Dx1 to Dxm, Dy1 to Dyn and Hv are terminals for electric connection having an airtight structure, which is arranged for electrically connecting the display panel to a not-shown electric circuit.
0102Terminals Dx1 to Dxm are electrically connected to the row-directional wiring 913 of the surface conduction electron-emitting devices, terminals Dy1 to Dyn to the column-directional wiring 914 of the surface conduction electron-emitting devices, and Hv to a metal back (a metallic membrane) of a face plate 919.
0103In order to evacuate the inside of an airtight vessel to a vacuum, the airtight vessel is assembled, a not-shown exhaust pipe is connected with a vacuum pump, and the inside of the airtight vessel is evacuated to a vacuum of 10<sup>-5</sup> [Pa] or lower. Afterwards, the exhaust pipe is sealed. Then, in order to keep the vacuum in the airtight vessel, a getter film (not shown) is formed just before or after sealing, on a predetermined position in the airtight vessel. The getter film is formed by heating and evaporating a getter material containing, for instance, Ba as a main component with a heater or high-frequency heating, and by the adsorption effect of the getter film, the inside of the airtight vessel is kept to a vacuum of 1×10<sup>-3</sup> to 1×10<sup>-5</sup> [Pa].
0104In the above described picture display unit using a display panel, when electric voltage is applied to each surface conduction electron-emitting device 912 through terminals outside a vessel, Dx1 to Dxm and Dy1 to Dyn, electrons are emitted from each surface conduction electron-emitting device 912. Concurrently with it, a high pressure of several hundreds [V] to several thousands [V] is applied to a metal back (metal membrane) 919 through the terminals outside the vessel Hv to accelerate the above described emitted electrons and make them collide with the inner surface of a face plate 917. Thereby, each phosphor of each color composing a phosphor layer 918 is activated to emit light, and images are displayed.
0105Normally, voltage applied to the surface conduction electron-emitting device 912 according to the present invention is around 12 to 16 [V], a distance d between a metal back (a metal membrane) 919 and the surface conduction electron-emitting device 912 is around 0.1 to 8 [mm], and voltage between the metal back (the metal membrane) 919 and the surface conduction electron-emitting device 912 is about 0.1 [kV] to 12 [kV].
0106A picture display unit and a spacer having a resistance film (an antistatic film) formed on the surface, which is used as a support structure therein, have been described above. However, according to the concept of the present invention, the spacer can be used not only for the picture display unit, but also as a light-emitting source substituted for a light-emitting diode of an optical printer constituted by a photosensitive drum and a light-emitting diode. In addition, if, at this time, the above described m lines of row-directional wiring and the n lines of column-directional wiring are appropriately selected, the spacer can be applied to not only a line-shaped light-emitting source but also a two-dimensional light-emitting source. In the above case, a usable body to be irradiated with electron can be not only a material directly emitting light such as a phosphor, but also a member on which a latent image is formed by the electrostatic charge of electrons. In addition, according to the concept of the present invention, the present invention can be applied to an electron-generating device, even when a material other than an image-forming member such as a phosphor is used as a body to be irradiated with the electrons emitted from an electron source, like in an electron microscope.
(Evaluation method for image)
0107A spacer substrate was prepared by forming a resistive film according to the present invention as an antistatic film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0108When the diselectrification capability of the spacer 801 is insufficient, as shown in <figref idref="f0006">FIG. 8</figref>, the trajectory of a beam is disturbed and the position of the lighting pixel which should be displayed at regular intervals moves. When a distance L between the original positions 802 of beams is defined as 1L, the deviation of a difference between the original position and the position 803 of a beam moved by a spacer is shown in ΔL.
0109The evaluation was carried out by placing a display device in an adequately bright room, and making the 50 subjects of adult men and women visually observe a display image at a place 1m apart from the panel face.
0110The observation result for the disarray of a display image due to the deviation of an electron beam was divided into 3 evaluation stages of "invisible" "visible but not annoying" and "visible and annoying", and a relationship between the stage and the deviation of the beam ΔL was determined. When the majority of the subjects answered "invisible", the deviation ΔL was 0 - 0.01L; when they answered "visible but not annoying", the deviation ΔL was 0.01 - 0.03L; and when they answered "visible", the deviation ΔL was 0.01L or more. The result is shown in Table 1.
0111The performance of a resistive film according to the present invention was evaluated by installing a spacer provided with the resistive film in a display device, and measuring the deviation of an electron beam ΔL in an image affected by the spacer. <tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="38mm" /><colspec colnum="2" colname="col2" colwidth="47mm" /><colspec colnum="3" colname="col3" colwidth="47mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><thead><row><entry align="center" valign="top">Visual evaluation</entry><entry align="center" valign="top">Deviation of electron beam ΔL</entry><entry align="center" valign="top">Deviation of electron beam [%]</entry><entry align="center" valign="top">Evaluation</entry></row></thead><tbody><row><entry align="center">Invisible</entry><entry align="center">0 - 0.01 L</entry><entry align="center">0-1%</entry><entry align="center">⊚</entry></row><row><entry align="center">Visible but not annoying</entry><entry align="center">0.01 - 0.03 L</entry><entry align="center">1-3%</entry><entry align="center">○</entry></row><row><entry align="center">Visible and annoying</entry><entry align="center">0.03L or more</entry><entry align="center">3% or more</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
Examples
0112Specific examples according to the present invention will be described below. Here, atomic% indicates the proportion of the number of atoms of monoatoms, and a Pt/Al weight ratio is calculated by (atomic% of Pt × atomic weight of Pt)/(atomic% of Al × atomic weight of Al).
(Example 1)
0113<maths id="math0001" num=""><math display="block"><mi>Pt</mi><mo>=</mo><mn>5</mn><mspace width="1em" /><mi>atomic</mi><mo>%</mo><mspace width="1em" /><mi>Pt</mi><mo>-</mo><mi>Al</mi><mo>-</mo><mi>melted alloy</mi></math><img file="EP1998355A2_D0001.tif" /></maths>
0114The raw materials of Pt and Al were weighed out so as to have the composition ratio of 5 atomic% Pt to 95 atomic% Al, and then were mixed. The mixed materials were melted in a vacuum melting furnace to produce an alloy. The alloy was cooled, and then was forge-rolled to further uniformize the component distribution. The melted alloy was pressure-baked in a vacuum, and was molded so as to acquire a predetermined plate thickness and shape suitable for a sputtering target, and the product became a Pt-Al-melted alloy mixture target. The density of the Pt-Al-melted alloy was 3.6 g/cm<sup>3</sup>.
0115A Pt-Al-melted alloy was installed as the target of a high-frequency sputtering apparatus shown in <figref idref="f0003">FIG. 3</figref>, the flow rate of N<sub>2</sub> was set to 100 sccm, and a Pt-Al mixture-nitrided film was formed with varied total pressures. The obtained Pt-Al mixture-nitrided film had the resistivity shown in <figref idref="f0004">FIG. 4</figref>.
0116Thus produced Pt-Al mixture-nitrided film was analyzed with the use of an RBS (Rutherford backscattering Spectrometory) method, and had the composition shown in Table 2. In addition, the density of the Pt-Al mixture-nitrided film was 3.5 g/cm<sup>3</sup>. <tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="7"><colspec colnum="1" colname="col1" colwidth="18mm" /><colspec colnum="2" colname="col2" colwidth="34mm" /><colspec colnum="3" colname="col3" colwidth="21mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="20mm" /><colspec colnum="7" colname="col7" colwidth="33mm" /><thead><row><entry morerows="1" align="center" valign="middle">Film type</entry><entry morerows="1" align="center" valign="middle">Pt content (atomic%)</entry><entry namest="col3" nameend="col6" align="center" valign="top">Concentration measured with RBS analysis (atomic%)</entry><entry morerows="1" align="center" valign="middle">Film density (g/cm<sup>3</sup>)</entry></row><row><entry align="center" valign="top">N</entry><entry align="center" valign="top">O</entry><entry align="center" valign="top">Al</entry><entry align="center" valign="top">Pt</entry></row></thead><tbody><row rowsep="0"><entry align="center">Pt-Al-N</entry><entry align="center">Pt = 3</entry><entry align="center">49.8</entry><entry align="center">0.3</entry><entry align="center">49.1</entry><entry align="center">0.8</entry><entry align="center">3.0</entry></row><row><entry align="center" /><entry align="center">Pt = 5</entry><entry align="center">50.0</entry><entry align="center">0.4</entry><entry align="center">47.1</entry><entry align="center">2.5</entry><entry align="center">3.5</entry></row></tbody></tgroup></table></tables>
(Example 2)
0117<maths id="math0002" num=""><math display="block"><mi>Pt</mi><mo>=</mo><mn>5</mn><mspace width="1em" /><mi>atomic</mi><mo>%</mo><mspace width="1em" /><mi>Pt</mi><mo>-</mo><mi>Al</mi><mo>-</mo><mi>melted alloy</mi></math><img file="EP1998355A2_D0002.tif" /></maths>
0118Similarly to the Example 1, raw materials were weighed out so as to have the composition ratio of 3 atomic% Pt to 97 atomic% Al, then, were mixed, melted, cooled, forge-rolled and pressure-baked. Thus, a Pt-Al-melted alloy mixture target was obtained. The density of the Pt-Al-melted alloy was 3.2 g/cm<sup>3</sup>.
0119Similarly to the Example 1, a Pt-Al mixture-nitrided film was formed, and had resistivity shown in <figref idref="f0004">FIG. 4</figref>.
0120Thus produced Pt-Al mixture-nitrided film was analyzed with the use of an RBS (Rutherford backscattering Spectrometory) method, and had a composition shown in Table 1. In addition, the density of the Pt-Al mixture-nitrided film was 3.0 g/cm<sup>3</sup>.
(Example 3)
0121<maths id="math0003" num=""><math display="block"><mi>Pt</mi><mo>=</mo><mn>5</mn><mspace width="1em" /><mi>atomic</mi><mo>%</mo><mspace width="1em" /><mi>Pt</mi><mo>-</mo><mi>AlN</mi><mo>-</mo><mi>sintered compact</mi></math><img file="EP1998355A2_D0003.tif" /></maths>
0122Instead of metallic aluminum, aluminum nitride was used as a raw material.
0123The powders of Pt and AlN were weighed out so as to have the composition ratio of 5 atomic% Pt to 95 atomic% AlN, and then were mixed. The powders were mixed with a ball mill in a non-oxidization atmosphere of nitrogen gas. After having been mixed, the powders were classified with a sieve to acquire a further uniformized granular form. Thus mixed powder was calcined in a vacuum.
0124Thus formed solid material was pulverized with the use of a ball mill in the non-oxidation atmosphere of nitrogen gas. After having been pulverized, the powders were classified with a sieve to acquire a further uniformized granular form.
0125The mixed powder obtained through pulverization was pressure-baked in a vacuum to provide a sintered compact. For the pressure-baking, a hot pressing process of heating the mixed powder to 1,500°C at the pressure of 2 MPa was employed. The sintered compact was formed so as to acquire a predetermined plate thickness and shape suitable for a sputtering target, and thus a Pt-AlN mixture sintered target was obtained. The Pt-AlN sintered compact had the density of 2.4 g/cm<sup>3</sup>.
0126Similarly to the Example 1, the N<sub>2</sub> flow rate was set to 100 sccm, and a Pt-AlN mixture-nitrided film was formed with varied total pressures. Then, the obtained film had resistivity shown in <figref idref="f0004">FIG. 5</figref>.
0127Thus produced Pt-AlN mixture-nitrided film was analyzed with the use of an RBS (Rutherford backscattering Spectrometory) method, and was proved to have the composition shown in Table 3. In addition, the Pt-AlN mixture-nitrided film had the density of 3.2 g/cm<sup>3</sup>. <tables id="tabl0003" num="0003"><table frame="all"><title>Table 3</title><tgroup cols="7"><colspec colnum="1" colname="col1" colwidth="18mm" /><colspec colnum="2" colname="col2" colwidth="34mm" /><colspec colnum="3" colname="col3" colwidth="21mm" /><colspec colnum="4" colname="col4" colwidth="20mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="20mm" /><colspec colnum="7" colname="col7" colwidth="33mm" /><thead><row><entry morerows="1" align="center" valign="middle">Film type</entry><entry morerows="1" align="center" valign="middle">Pt content (atomic%)</entry><entry namest="col3" nameend="col6" align="center" valign="top">Concentration measured with RBS analysis (atomic%)</entry><entry morerows="1" align="center" valign="middle">Film density (g/cm<sup>3</sup>)</entry></row><row><entry align="center" valign="top">N</entry><entry align="center" valign="top">O</entry><entry align="center" valign="top">Al</entry><entry align="center" valign="top">Pt</entry></row></thead><tbody><row rowsep="0"><entry align="center">Pt-Al-N</entry><entry align="center">Pt = 3</entry><entry align="center">45.6</entry><entry align="center">8.5</entry><entry align="center">45.0</entry><entry align="center">0.9</entry><entry align="center">2.8</entry></row><row><entry align="center" /><entry align="center">Pt = 5</entry><entry align="center">45.7</entry><entry align="center">9.0</entry><entry align="center">43.0</entry><entry align="center">2.3</entry><entry align="center">3.2</entry></row></tbody></tgroup></table></tables>
(Example 4)
0128<maths id="math0004" num=""><math display="block"><mi>Pt</mi><mo>=</mo><mn>3</mn><mspace width="1em" /><mi>atomic</mi><mo>%</mo><mspace width="1em" /><mi>Pt</mi><mo>-</mo><mi>AlN sintered compact</mi></math><img file="EP1998355A2_D0004.tif" /></maths>
0129Similarly to the Example 3, instead of metallic aluminum, aluminum nitride was used as a raw material, and the raw materials were weighed out so as to have the composition ratio of 3 atomic% Pt to 97 atomic% AlN, then, were mixed, calcinated, pulverized, and pressure-baked. Thus, a Pt-AlN mixture sintered target was obtained. The Pt-AlN sintered compact had the density of 2.0 g/cm<sup>3</sup>.
0130Similarly to the Example 1, a N<sub>2</sub> flow rate was set to 100 sccm, and a Pt-AlN mixture-nitrided film was formed with varied total pressures. Then, the obtained film had resistivity shown in <figref idref="f0004">FIG. 5</figref>.
0131Thus produced Pt-AlN mixture-nitrided film was analyzed with the use of an RBS (Rutherford backscattering) method, and was proved to have the composition shown in Table 3. In addition, the Pt-AlN mixture-nitrided film had the density of 2.8 g/cm<sup>3</sup>.
(Comparative Example 1)
0132Comparison with binary target: Pt = 5 atomic% nitrided film
0133The targets made of elemental Pt and elemental Al were separately prepared. Similarly to the Example 1, a Pt target and an Al target were each installed as the target of a high-frequency sputtering apparatus. Under the conditions of the total pressure of 0.2 Pa and the N<sub>2</sub> flow rate of 100 sccm, the power for electrifying each target was adjusted. The film was formed so as to acquire the same Pt content (Pt = 2.5 atomic%) as the formed film with the use of the Pt = 5 atomic% Pt-Al target.
0134The films were repeatedly formed under thus adjusted equal conditions, but the produced Pt-Al mixture-nitrided film had varied resistivities as are shown in <figref idref="f0005">FIG. 6</figref>.
(Comparative Example 2)
0135<maths id="math0005" num=""><math display="block"><mi>Comparison with binary target</mi><mo>:</mo><mi>Pt</mi><mo>=</mo><mn>3</mn><mspace width="1em" /><mi>atomic</mi><mo>%</mo><mspace width="1em" /><mi>nitrited film</mi></math><img file="EP1998355A2_D0005.tif" /></maths>
0136The targets made of elemental Pt and elemental Al were separately prepared. Similarly to the Example 1, a Pt target and an Al target were each installed as the target of a high-frequency sputtering apparatus. Under the conditions of the total pressure of 0.2 Pa and the N<sub>2</sub> flow rate of 100 sccm, the power for electrifying each target was adjusted. The conditions were adjusted so that the film could acquire the same Pt content (Pt = 0.8 atomic%) as the formed film with the use of a Pt = 3 atomic% Pt-Al target.
0137The films were repeatedly formed under thus. adjusted equal conditions, but the produced Pt-Al mixture-nitrided film had the variation of resistivities as shown in <figref idref="f0005">FIG. 6</figref>.
(Example 5)
0138As a target used for a high-frequency sputtering apparatus shown in <figref idref="f0002">FIG. 2</figref>, a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Al and the diameter of 8 inches produced in the manner of Example 1 was installed. Under the nitrogen/argon mixed gas flow rate of N<sub>2</sub> = 70 sccm and Ar = 30 sccm and the sputtering pressure of 1.0 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0139A glass substrate was introduced into a film-forming chamber, and a film was formed on it. Sputtering time was 30 minutes. Thus obtained resistive film had the film thickness of 200 nm, and the resistivity of 2×10<sup>9</sup> Ωcm.
0140Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM ( transmission electron microscope), and showed the diameter of 0.4 nm.
(Example 6)
0141A Pt-Al mixture target was set which had the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. Under the nitrogen/argon mixed gas flow rate of N<sub>2</sub>=70 sccm and Ar=30 sccm and the sputtering pressure of 0.5 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0142A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 25 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>9</sup> Ωcm.
0143Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 0.5 nm.
(Example 7)
0144A Pt-Al mixture target was set which had the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. Under the nitrogen/argon mixed gas flow rate of N<sub>2</sub>=70 sccm and Ar=30 sccm and the sputtering pressure of 0.3 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0145A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 20 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 8x10<sup>8</sup> Ωcm.
0146Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 0.6 nm.
(Example 8)
0147A Pt-Al mixture target was set which had the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. Under the nitrogen/argon mixed gas flow rate of N<sub>2</sub>=70 sccm and Ar=30 sccm and the sputtering pressure of 1.0 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0148A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 30 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>4</sup> Ωcm.
0149Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 9 nm.
(Example 9)
0150A Pt-Al mixture target was set which had the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. Under the nitrogen/argon mixed gas flow rate of N<sub>2</sub>=70 sccm and Ar=30 sccm and the sputtering pressure of 0.5 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0151A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 25 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>4</sup> Ωcm.
0152Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 10 nm.
(Example 10)
0153A Pt-Al mixture target was set which had the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. Under the nitrogen/argon mixed gas flow rate of N<sub>2</sub>=70 sccm and Ar=30 sccm and the sputtering pressure of 0.3 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0154A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 20 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>0</sup> Ωcm.
0155Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 11 nm.
(Example 11)
0156A film was formed with the use of a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Al and the diameter of 8 inches, at the nitrogen-gas flow rate of N<sub>2</sub>=100 sccm. A sputtering pressure was set to 1.0 Pa, and an electrification power to 2,400 W.
0157After the sputtering time of 70 minutes, a resistive film having the thickness of 200 nm was obtained. The resistive film had the resistivity of 1×10<sup>11</sup> Ωcm.
0158Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 0.8 nm.
(Example 12)
0159A film was formed with the use of a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Δl and the diameter of 8 inches, at the nitrogen-gas flow rate of N<sub>2</sub>=100 sccm. A sputtering pressure was set to 0.5 Pa, and an electrification power to 2,400 W.
0160After the sputtering time of 65 minutes, a resistive film having the film thickness of 200 nm was obtained. The resistive film had the resistivity of 1×10<sup>11</sup> Ωcm.
0161Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 1 nm.
(Example 13)
0162A film was formed with the use of a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Al and the diameter of 8 inches, at the nitrogen-gas flow rate of N<sub>2</sub>=100 sccm. A sputtering pressure was set to 0.3 Pa, and an electrification power to 2,400 W.
0163After the sputtering time of 60 minutes, a resistive film having the film thickness of 200 nm was obtained. The resistive film had the resistivity of 8×10<sup>10</sup> Ωcm.
0164Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the diameter of 2 nm.
(Example 14)
0165A film was formed with the use of a Pt-Al mixture target having the composition ratio of 30 atomic% Pt to 70 atomic% Al and the diameter of 8 inches, at the nitrogen-gas flow rate of N<sub>2</sub>=100 sccm. A sputtering pressure was set to 1.0 Pa, and an electrification power to 2,400 W.
0166After the sputtering time of 70 minutes, a resistive film having the thickness of 200 nm was obtained. The resistive film had the resistivity of 1×10<sup>4</sup> Ωcm.
0167Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 9 nm.
(Example 15)
0168A film was formed with the use of a Pt-Al mixture target having the composition ratio of 30 atomic% Pt to 70 atomic% Al and the diameter of 8 inches, at the nitrogen-gas flow rate of N<sub>2</sub>=100 sccm. A sputtering pressure was set to 0.5 Pa, and an electrification power to 2,400 W.
0169After the sputtering time of 65 minutes, a resistive film having the film thickness of 200 nm was obtained. The resistive film had the resistivity of 1×10<sup>4</sup> Ωcm.
0170Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 10 nm.
(Example 16)
0171A film was formed with the use of a Pt-Al mixture target having the composition ratio of 30 atomic% Pt to 70 atomic% Al and the diameter of 8 inches, at the nitrogen-gas flow rate of N<sub>2</sub>=100 sccm. A sputtering pressure was set to 0.3 Pa, and an electrification power to 2,400 W.
0172After the sputtering time of 60 minutes, a resistive film having the film thickness of 200 nm was obtained. The resistive film had the resistivity of 1×10<sup>2</sup> Ωcm.
0173Thus produced Pt-Al mixture-nitrided film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride through a TEM (transmission electron microscope), and showed the average particle diameter of 11 nm.
(Example 17)
0174A Pt-Al mixture target was set which had the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. Under the oxygen gas flow rate of O<sub>2</sub>=10 sccm and the sputtering pressure of 1.0 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0175A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 70 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 5×10<sup>11</sup> Ωcm.
0176Thus produced Pt-Al mixture-oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 0.4 nm.
(Example 18)
0177A Pt-Al mixture target was set which had the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. Under the oxygen gas flow rate of O<sub>2</sub>=100 sccm and the sputtering pressure of 0.5 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0178A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 65 minutes, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>11</sup> Ωcm.
0179Thus produced Pt-Al mixture-oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 0.5 nm.
(Example 19)
0180A Pt-Al mixture target was set which had the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. Under the oxygen gas flow rate of O<sub>2</sub>=100 sccm and the sputtering pressure of 0.3 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0181A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 60 minutes, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>11</sup> Ωcm.
0182Thus produced Pt-Al mixture-oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 0.6 nm.
(Example 20)
0183A Pt-Al mixture target was set which had the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. Under the oxygen gas flow rate of O<sub>2</sub>=100 sccm and the sputtering pressure of 1.0 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0184A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 70 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>8</sup> Ωcm.
0185Thus produced Pt-Al mixture-oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum oxide through a TEM (transmission electron microscope), and showed the diameter of 8 nm.
(Example 21)
0186A Pt-Al mixture target was set which had the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. Under the oxygen gas flow rate of O<sub>2</sub>=100 sccm and the sputtering pressure of 0.5 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0187A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 65 minutes, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>7</sup> Ωcm.
0188Thus produced Pt-Al mixture-oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum oxide through a TEM (transmission electron microscope.), and showed the average particle diameter of 9 nm.
(Example 22)
0189A Pt-Al mixture target was set which had the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. Under the oxygen gas flow rate of O<sub>2</sub>=100 sccm and the sputtering pressure of 0.3 Pa, the above described Pt-Al mixture target was sputtered with the high-frequency electrification power of 2,400 W.
0190A glass substrate was introduced into a film-forming chamber, and the film was formed on it. After the sputtering time of 60 minutes, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>6</sup> Ωcm.
0191Thus produced Pt-Al mixture-oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 10 nm.
(Example 23)
0192A film was formed with the use of a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. The film was formed at the oxygen/nitrogen mixed gas flow rate of O<sub>2</sub>=2 sccm and N<sub>2</sub>=98 sccm. A sputtering pressure was set to 1.0 Pa, and an electrification power to 2,400 W.
0193After the sputtering time of 35 minutes, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 2×10<sup>12</sup> Ωcm.
0194Thus produced Pt-Al mixture-nitrided/oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride and aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 0.4 nm.
(Example 24)
0195A film was formed with the use of a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. The film was formed at the oxygen/nitrogen mixed gas flow rate of O<sub>2</sub>=2 sccm and N<sub>2</sub>=98 sccm. A sputtering pressure was set to 0.5 Pa, and an electrification power to 2,400 W.
0196After the sputtering time of 30 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>11</sup> Ωcm.
0197Thus produced Pt-Al mixture-nitrided/oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride and aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 0.5 nm.
(Example 25)
0198A film was formed with the use of a Pt-Al mixture target having the composition ratio of 2 atomic% Pt to 98 atomic% Al, and the diameter of 8 inches. The film was formed at the oxygen/nitrogen mixed gas flow rate of O<sub>2</sub>=2 sccm and N<sub>2</sub>=98 sccm. A sputtering pressure was set to 0.3 Pa, and an electrification power to 2,400 W.
0199The sputtering time was 25 minutes. Then, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>11</sup> Ωcm.
0200Thus produced Pt-Al mixture-nitrided/oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride and aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 0.6 nm.
(Example 26)
0201A film was formed with the use of a Pt-Al mixture target having the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. The film was formed at the oxygen/nitrogen mixed gas flow rate of O<sub>2</sub>=2 sccm and N<sub>2</sub>=98 sccm. A sputtering pressure was set to 1.0 Pa, and an electrification power to 2,400 W.
0202After the sputtering time of 35 minutes, a resistive film having the film thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1x10<sup>5</sup> Ωcm.
0203Thus produced Pt-Al mixture-nitrided/oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride and aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 9 nm.
(Example 27)
0204A film was formed with the use of a Pt-Al mixture target having the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. The film was formed at the oxygen/nitrogen mixed gas flow rate of O<sub>2</sub>=2 sccm and N<sub>2</sub>=98 sccm. A sputtering pressure was set to 0.5 Pa, and an electrification power to 2,400 W.
0205After the sputtering time of 30 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 1×10<sup>4</sup> Ωcm.
0206Thus produced Pt-Al mixture-nitrided/oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride and aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 10 nm.
(Example 28)
0207A film was formed with the use of a Pt-Al mixture target having the composition ratio of 30 atomic% Pt to 70 atomic% Al, and the diameter of 8 inches. The film was formed at the oxygen/nitrogen mixed gas flow rate of O<sub>2</sub>=2 sccm and N<sub>2</sub>=98 sccm. A sputtering pressure was set to 0.3 Pa, and an electrification power to 2,400 W.
0208After the sputtering time of 25 minutes, a resistive film having the thickness of 200 nm was obtained. The obtained resistive film had the resistivity of 5×10<sup>3</sup> Ωcm.
0209Thus produced Pt-Al mixture-nitrided/oxidized film was subjected to the measurement of the average particle diameter of platinum particles dispersed in the medium of aluminum nitride and aluminum oxide through a TEM (transmission electron microscope), and showed the average particle diameter of 11 nm.
0210A spacer substrate was prepared by forming each resistive film shown in the above described samples 5 to 28 as an antistatic film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment. The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0211A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0212A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0213The results are shown in Table 4. <tables id="tabl0004" num="0004"><table frame="all"><title>Table 4</title><tgroup cols="8"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="22mm" /><colspec colnum="4" colname="col4" colwidth="17mm" /><colspec colnum="5" colname="col5" colwidth="22mm" /><colspec colnum="6" colname="col6" colwidth="21mm" /><colspec colnum="7" colname="col7" colwidth="23mm" /><colspec colnum="8" colname="col8" colwidth="23mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">TGT composition</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Sputtering pressure [Pa]</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry>Example 5</entry><entry morerows="5" align="center" valign="middle">Pt-Al-N</entry><entry morerows="2" align="center" valign="middle">Pt:2% Al:98%</entry><entry morerows="5" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">1.0 Pa</entry><entry align="center">2.E+09</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry>Example 6</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+09</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry>Example 7</entry><entry align="center">0.3 a</entry><entry align="center">8.E+08</entry><entry align="center">0.6</entry><entry align="center">○</entry></row><row><entry>Example 8</entry><entry morerows="2" valign="middle">Pt:30% Al:70%</entry><entry align="center">1.0 Pa</entry><entry align="center">1.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry>Example 9</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry>Example 10</entry><entry align="center">0.3 a</entry><entry align="center">1.E+03</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry>Example 11</entry><entry morerows="5" align="center" valign="middle">Pt-Al-N</entry><entry morerows="2" align="center" valign="middle">Pt2% Al:98%</entry><entry morerows="5" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.0 Pa</entry><entry align="center">1.E+11</entry><entry align="center">0.8</entry><entry align="center">○</entry></row><row><entry>Example 12</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+11</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry>Example 13</entry><entry align="center">0.3 a</entry><entry align="center">8.E+10</entry><entry align="center">2</entry><entry align="center">⊚</entry></row><row><entry>Example 14</entry><entry morerows="2" align="center" valign="middle">Pt:30% Al:70%</entry><entry align="center">1.0 Pa</entry><entry align="center">1.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry>Example 15</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry>Example 16</entry><entry align="center">0.3 a</entry><entry align="center">1.E+02</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry>Example 17</entry><entry morerows="5" align="center" valign="middle">Pt-Al-O</entry><entry morerows="2" align="center" valign="middle">Pt:2% Al:98%</entry><entry morerows="5" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.0 Pa</entry><entry align="center">5.E+11</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry>Example 18</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry>Example 19</entry><entry align="center">0.3 a</entry><entry align="center">1.E+11</entry><entry align="center">0.6</entry><entry align="center">○</entry></row><row><entry>Example 20</entry><entry morerows="2" align="center" valign="middle">Pt:30% Al:70%</entry><entry align="center">1.0 Pa</entry><entry align="center">1.E+08</entry><entry align="center">8</entry><entry align="center">⊚</entry></row><row><entry>Example 21</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+07</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry>Example 22</entry><entry align="center">0.3 a</entry><entry align="center">1.E+06</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry>Example 23</entry><entry morerows="5" align="center" valign="middle">Pt-Al-N-O</entry><entry morerows="2" align="center" valign="middle">Pt:2% Al:98%</entry><entry morerows="5" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">1.0 Pa</entry><entry align="center">2.E+12</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry>Example 24</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry>Example 25</entry><entry align="center">0.3 a</entry><entry align="center">1.E+11</entry><entry align="center">0.6</entry><entry align="center">○</entry></row><row><entry>Example 26</entry><entry morerows="2" align="center" valign="middle">Pt:30% Al:70%</entry><entry align="center">1.0 Pa</entry><entry align="center">1.E+05</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry>Example 27</entry><entry align="center">0.5 Pa</entry><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">O</entry></row><row><entry>Example 28</entry><entry align="center">0.3 a</entry><entry align="center">5.E+03</entry><entry align="center">11</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
(Example 29)
0214A film was formed with the use of a Pt-Ge mixture target prepared so as to have an adjusted composition ratio and the diameter of 8 inches.
0215The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 Pa to 1.5 Pa, and an electrification power to 2,400 W.
0216A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0217The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of platinum particles in a medium was determined.
0218A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using a surface conduction electron-emitting device, which is the present embodiment. The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0219A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0220A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0221The results are shown in Table 5. <tables id="tabl0005" num="0005"><table frame="all"><title>Table 5</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 29</entry><entry morerows="2" align="center" valign="middle">Pt-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">2.E+09</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+09</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry align="center">5.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry align="center">8.E+10</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry align="center">8.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Ge-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.E+14</entry><entry align="center">0.3</entry><entry align="center">×</entry></row><row><entry align="center">1.E+08</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+07</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Ge-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.6</entry><entry align="center">○</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry align="center">5.E+03</entry><entry align="center">11</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
(Example 30)
0222A film was formed with the use of a Pt-Si mixture target prepared so as to have an adjusted composition ratio and the diameter of 8 inches.
0223The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0224A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0225The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of platinum particles in a medium was determined.
0226A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0227The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0228A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0229A spacer provided with a resistive film having a resistivity ρ of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0230The results are shown in Table 6. <tables id="tabl0006" num="0006"><table frame="all"><title>Table 6</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 30</entry><entry morerows="2" align="center" valign="middle">Pt-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">1.E+09</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">5.E+08</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry align="center">3.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry align="center">4.E+10</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry align="center">4.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Si-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.E+14</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+08</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+07</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Si-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">5.E+11</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry align="center">3.E+03</entry><entry align="center">11</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
(Example 31)
0231A film was formed with the use of a Pt-Mg mixture target prepared so as to have an adjusted composition ratio and the diameter of 8 inches.
0232The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0233A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0234The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of platinum particles in a medium was determined.
0235A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0236The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0237A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0238A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing platinum particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0239The results are shown in Table 7. <tables id="tabl0007" num="0007"><table frame="all"><title>Table 7</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 31</entry><entry morerows="2" align="center" valign="middle">Pt-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">1.E+11</entry><entry align="center">0.3</entry><entry align="center">×</entry></row><row><entry align="center">5.E+10</entry><entry align="center">0.8</entry><entry align="center">○</entry></row><row><entry align="center">1.E+04</entry><entry align="center">8</entry><entry align="center">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">O</entry></row><row><entry align="center">4.E+10</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Mg-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.E+14</entry><entry align="center">0.2</entry><entry align="center">×</entry></row><row><entry align="center">1.E+08</entry><entry align="center">4</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+07</entry><entry align="center">5</entry><entry align="center">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Pt-Mg-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">6.E+05</entry><entry align="center">8</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">O</entry></row><row><entry align="center">3.E+03</entry><entry align="center">12</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
(Example 32)
0240A film was formed with the use of an Au-Al mixture target having a composition ratio adjusted so as to comprise gold for a particle material, and aluminum nitride, aluminum oxide or aluminum nitride/oxide for a medium, and having the diameter of 8 inches.
0241The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0242A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0243The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of gold particles in a medium was determined.
0244A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0245The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0246A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0247A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0248The results are shown in Table 8. <tables id="tabl0008" num="0008"><table frame="all"><title>Table 8</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 32</entry><entry morerows="2" align="center" valign="middle">Au-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">O</entry></row><row><entry align="center">1.E+09</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry align="center">6.E+01</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.6</entry><entry align="center">○</entry></row><row><entry align="center">1.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry align="center">9.E+02</entry><entry align="center">12</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Al-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.E+14</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+08</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry align="center">1.E+07</entry><entry align="center">12</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Al-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">1.E+12</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry align="center">6.E+03</entry><entry align="center">13</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
(Example 33)
0249A film was formed with the use of an Au-Ge mixture target having a composition ratio adjusted so as to comprise gold for a particle material, and germanium nitride, germanium oxide or germanium nitride/oxide for a medium, and having the diameter of 8 inches.
0250The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0251A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0252The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of gold particles in a medium was determined.
0253A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0254The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0255A spacer provided with a resistive film having a resistivity ρ of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0256A spacer provided with a resistive film having a resistivity ρ of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0257The results are shown in Table 9. <tables id="tabl0009" num="0009"><table frame="all"><title>Table 9</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 33</entry><entry morerows="2" align="center" valign="middle">Au-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">2.E+09</entry><entry align="center">0.5</entry><entry align="center">O</entry></row><row><entry align="center">1.E+09</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry align="center">6.E+01</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">O</entry></row><row><entry align="center">1.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry align="center">9.E+02</entry><entry align="center">12</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Ge-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.E+14</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+08</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry align="center">1.E+07</entry><entry align="center">12</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Ge-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.7</entry><entry align="center">○</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row><row><entry align="center">6.E+03</entry><entry align="center">13</entry><entry align="center">×</entry></row></tbody></tgroup></table></tables>
(Example 34)
0258A film was formed with the use of an Au-Si mixture target having a composition ratio adjusted so as to comprise gold for a particle material, and silicon nitride, silicon oxide or silicon nitride/oxide for a medium, and having the diameter of 8 inches.
0259The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0260A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0261The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of gold particles in a medium was determined.
0262A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0263The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0264A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0265A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0266The results are shown in Table 10. <tables id="tabl0010" num="0010"><table frame="all"><title>Table 10</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="top" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 34</entry><entry morerows="2" align="center" valign="middle">Au-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center">1.E+09</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry align="center">6.E+08</entry><entry align="center">1</entry><entry align="center">⊚</entry></row><row><entry align="center">3.E+01</entry><entry align="center">11</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.5</entry><entry align="center">○</entry></row><row><entry align="center">1.E+04</entry><entry align="center">9</entry><entry align="center">⊚</entry></row><row><entry align="center">4.E+01</entry><entry align="center">12</entry><entry align="center">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Si-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center">1.E+14</entry><entry align="center">0.4</entry><entry align="center">×</entry></row><row><entry align="center">1.E+08</entry><entry align="center">7</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+07</entry><entry align="center">8</entry><entry align="center">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Si-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center">1.E+11</entry><entry align="center">0.7</entry><entry align="center">○</entry></row><row><entry align="center">1.E+05</entry><entry align="center">8</entry><entry align="center">⊚</entry></row><row><entry align="center">1.E+04</entry><entry align="center">10</entry><entry align="center">○</entry></row></tbody></tgroup></table></tables>
(Example 35)
0267A film was formed with the use of an Au-Mg mixture target having a composition ratio adjusted so as to comprise gold for a particle material, and magnesium nitride, magnesium oxide or magnesium nitride/oxide for a medium, and having the diameter of 8 inches.
0268The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0269A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0270The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of gold particles in a medium was determined.
0271A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0272The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0273A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0274A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing gold particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0275The results are shown in Table 11. <tables id="tabl0011" num="0011"><table frame="all"><title>Table 11</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 35</entry><entry morerows="2" align="center" valign="middle">Au-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">6.E+10</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">4.E+10</entry><entry align="center" valign="middle">0.7</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+01</entry><entry align="center" valign="middle">12</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Mg-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14<<</entry><entry align="center" valign="middle">0.2</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">1.E+08</entry><entry align="center" valign="middle">5</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+07</entry><entry align="center" valign="middle">6</entry><entry align="center" valign="middle">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Au-Mg-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">7.E+05</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">3.E+03</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 36)
0276A film was formed with the use of an Ag-Al mixture target having a composition ratio adjusted so as to comprise silver for a particle material, and aluminum nitride, aluminum oxide or aluminum nitride/oxide for a medium, and having the diameter of 8 inches.
0277The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0278A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0279The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silver particles in a medium was determined.
0280A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0281The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0282A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0283A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0284The results are shown in Table 12. <tables id="tabl0012" num="0012"><table frame="all"><title>Table 12</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 36</entry><entry morerows="2" align="center" valign="middle">Ag-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">2.E+11</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+09</entry><entry align="center" valign="middle">0.7</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+02</entry><entry align="center" valign="middle">13</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+10</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+03</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Al-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+08</entry><entry align="center" valign="middle">13</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+07</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Al-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">2.E+12</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+04</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row></tbody></tgroup></table></tables>
(Example 37)
0285A film was formed with the use of an Ag-Ge mixture target having a composition ratio adjusted so as to comprise silver for a particle material, and germanium nitride, germanium oxide or germanium nitride/oxide for a medium, and having the diameter of 8 inches.
0286The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0287A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0288The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silver particles in a medium was determined.
0289A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0290The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0291A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0292A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0293The results are shown in Table 13. <tables id="tabl0013" num="0013"><table frame="all"><title>Table 13</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 37</entry><entry morerows="2" align="center" valign="middle">Ag-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">4.E+09</entry><entry align="center" valign="middle">0.6</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+09</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+02</entry><entry align="center" valign="middle">13</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">5.E+04</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+03</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Ge-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+08</entry><entry align="center" valign="middle">13</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+07</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Ge-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.9</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+03</entry><entry align="center" valign="middle">16</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 38)
0294A film was formed with the use of an Ag-Si mixture target having a composition ratio adjusted so as to comprise silver for a particle material, and silicon nitride, silicon oxide or silicon nitride/oxide for a medium, and having the diameter of 8 inches.
0295The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0296A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0297The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silver particles in a medium was determined.
0298A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0299The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0300A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0301A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0302The results are shown in Table 14. <tables id="tabl0014" num="0014"><table frame="all"><title>Table 14</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 38</entry><entry morerows="2" align="center" valign="middle">Ag-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">2.E+09</entry><entry align="center" valign="middle">0.6</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+09</entry><entry align="center" valign="middle">0.7</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">6.E+01</entry><entry align="center" valign="middle">13</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">O</entry></row><row><entry align="center" valign="middle">8.E+10</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">8.E+01</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Si-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14<<</entry><entry align="center" valign="middle">0.7</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+08</entry><entry align="center" valign="middle">8</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+07</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Si-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.9</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+04</entry><entry align="center" valign="middle">11</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 39)
0303A film was formed with the use of an Ag-Mg mixture target having a composition ratio adjusted so as to comprise silver for a particle material, and magnesium nitride, magnesium oxide or magnesium nitride/oxide for a medium, and having the diameter of 8 inches.
0304The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0305A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0306The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silver particles in a medium was determined.
0307A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0308The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0309A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0310A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silver particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0311The results are shown in Table 15. <tables id="tabl0015" num="0015"><table frame="all"><title>Table 15</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 39</entry><entry morerows="2" align="center" valign="middle">Ag-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">2.E+11</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">12</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">8.E+10</entry><entry align="center" valign="middle">0.9</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">4.E+01</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Mg-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14<<</entry><entry align="center" valign="middle">0.3</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">2.E+08</entry><entry align="center" valign="middle">6</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+07</entry><entry align="center" valign="middle">7</entry><entry align="center" valign="middle">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Ag-Mg-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">1.E+06</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">6.E+03</entry><entry align="center" valign="middle">17</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 40)
0312A film was formed with the use of a Ge-Al mixture target having a composition ratio adjusted so as to comprise germanium for a particle material, and aluminum nitride, aluminum oxide or aluminum nitride/oxide for a medium, and having the diameter of 8 inches.
0313The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0314A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0315The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of germanium particles in a medium was determined.
0316A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0317The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0318A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing germanium particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0319A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing germanium particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0320The results are shown in Table 16. <tables id="tabl0016" num="0016"><table frame="all"><title>Table 16</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 40</entry><entry morerows="2" align="center" valign="middle">Ge-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">4.E+11</entry><entry align="center" valign="middle">0.7</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">4.E+09</entry><entry align="center" valign="middle">1</entry><entry align="center">⊚</entry></row><row><entry align="center" valign="middle">2.E+02</entry><entry align="center" valign="middle">16</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">4.E+04</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">3.E+03</entry><entry align="center" valign="middle">17</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Al-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14<<</entry><entry align="center" valign="middle">0.9</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">4.E+08</entry><entry align="center" valign="middle">16</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">4.E+07</entry><entry align="center" valign="middle">17</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Al-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+04</entry><entry align="center" valign="middle">12</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 41)
0321A film was formed with the use of a Ge-Si mixture target having a composition ratio adjusted so as to comprise germanium for a particle material, and silicon nitride, silicon oxide or silicon nitride/oxide for a medium, and having the diameter of 8 inches.
0322The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0323A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0324The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of germanium particles in a medium was determined.
0325A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0326The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0327A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing germanium particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0328A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing germanium particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0329The results are shown in Table 17. <tables id="tabl0017" num="0017"><table frame="all"><title>Table 17</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 41</entry><entry morerows="2" align="center" valign="middle">Ge-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">4.E+09</entry><entry align="center" valign="middle">0.7</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+09</entry><entry align="center" valign="middle">0.9</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+02</entry><entry align="center" valign="middle">16</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Si-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+02</entry><entry align="center" valign="middle">17</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Si-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">4.E+08</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">4.E+07</entry><entry align="center" valign="middle">11</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Si-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">4.E+04</entry><entry align="center" valign="middle">13</entry><entry align="center" valign="middle">x</entry></row></tbody></tgroup></table></tables>
(Example 42)
0330A film was formed with the use of a Ge-Mg mixture target having a composition ratio adjusted so as to comprise germanium for a particle material, and magnesium nitride, magnesium oxide or magnesium nitride/oxide for a medium, and having the diameter of 8 inches.
0331The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0332A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0333The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of germanium particles in a medium was determined.
0334A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0335The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0336A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing germanium particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0337A spacer provided with a resistive film having a resistivity ρ of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing germanium particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0338The results are shown in Table 18. <tables id="tabl0018" num="0018"><table frame="all"><title>Table 18</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 42</entry><entry morerows="2" align="center" valign="middle">Ge-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+10</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+04</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">8.E+01</entry><entry align="center" valign="middle">17</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Mg-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14<<</entry><entry align="center" valign="middle">0.3</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">4.E+08</entry><entry align="center" valign="middle">7</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">4.E+07</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry morerows="2" align="center" valign="middle">Ge-Mg-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">2.E+06</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">2.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+02</entry><entry align="center" valign="middle">20</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 43)
0339A film was formed with the use of a Si-Al mixture target having a composition ratio adjusted so as to comprise silicon for a particle material, and aluminum nitride, aluminum oxide or aluminum nitride/oxide for a medium, and having the diameter of 8 inches.
0340The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0341A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0342The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silicon particles in a medium was determined.
0343A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0344The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0345A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silicon particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0346A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silicon particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0347The results are shown in Table 19. <tables id="tabl0019" num="0019"><table frame="all"><title>Table 19</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="18mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 43</entry><entry morerows="2" align="center" valign="middle">Si-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.8</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">9.E+09</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">5.E+02</entry><entry align="center" valign="middle">19</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Al-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">9.E+04</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">7.E+03</entry><entry align="center" valign="middle">21</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Al-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">9.E+08</entry><entry align="center" valign="middle">19</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">9.E+07</entry><entry align="center" valign="middle">21</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Al-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">5.E+04</entry><entry align="center" valign="middle">14</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 44)
0348A film was formed with the use of an Si-Ge mixture target having a composition ratio adjusted so as to comprise silicon for a particle material, and germanium nitride, germanium oxide or germanium nitride/oxide for a medium, and having the diameter of 8 inches.
0349The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0350A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0351The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silicon particles in a medium was determined.
0352A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0353The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0354A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silicon particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0355A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silicon particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0356The results are shown in Table 20. <tables id="tabl0020" num="0020"><table frame="all"><title>Table 20</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 44</entry><entry morerows="2" align="center" valign="middle">Si-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">2.E+10</entry><entry align="center" valign="middle">0.8</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">9.E+09</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">5.E+02</entry><entry align="center" valign="middle">19</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Ge-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">5.E+11</entry><entry align="center" valign="middle">0.1</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">7.E+03</entry><entry align="center" valign="middle">21</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Ge-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">9.E+08</entry><entry align="center" valign="middle">19</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">9.E+07</entry><entry align="center" valign="middle">21</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Ge-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">9.E+10</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">5.E+03</entry><entry align="center" valign="middle">23</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
(Example 45)
0357A film was formed with the use of a Si-Mg mixture target having a composition ratio adjusted so as to comprise silicon for a particle material, and magnesium nitride, magnesium oxide or magnesium nitride/oxide for a medium, and having the diameter of 8 inches.
0358The following 4 kinds of gas types were used in order to form the film: a nitrogen/Ar mixed gas, nitrogen gas, oxygen gas and an oxygen/nitrogen mixed gas. A sputtering pressure was set to 0.3 to 1.5 Pa, and an electrification power to 2,400 W.
0359A sputtering time of period was appropriately adjusted so that film thickness can be 200 nm.
0360The resistivities of these resistive films were measured. In addition, by using a TEM (transmission electron microscope), an average particle diameter of silicon particles in a medium was determined.
0361A spacer substrate was prepared by forming each resistive film on a glass substrate, and was used as a spacer in a picture display unit using the surface conduction electron-emitting device, which is the present embodiment.
0362The influence of the spacer on an image was evaluated by measuring the deviation of an electron beam ΔL.
0363A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silicon particles with diameters in a range of 0.5 to 10 nm, showed the deviation of an electron beam ΔL of 3% or less (0.03L or less) and an adequate display image.
0364A spacer provided with a resistive film having a resistivity p of 1×10<sup>4</sup> to 1×10<sup>11</sup> Ωcm and containing silicon particles with diameters in a range of 1 to 9 nm, showed the deviation of an electron beam ΔL of 1% or less (0.01L or less) and a particularly adequate display image.
0365The results are shown in Table 21. <tables id="tabl0021" num="0021"><table frame="all"><title>Table 21</title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="21mm" /><colspec colnum="2" colname="col2" colwidth="20mm" /><colspec colnum="3" colname="col3" colwidth="17mm" /><colspec colnum="4" colname="col4" colwidth="29mm" /><colspec colnum="5" colname="col5" colwidth="48mm" /><colspec colnum="6" colname="col6" colwidth="29mm" /><thead><row><entry align="center" valign="middle" /><entry align="center" valign="middle">Film type</entry><entry align="center" valign="middle">Gas type</entry><entry align="center" valign="middle">Resistivity [Ωcm]</entry><entry align="center" valign="middle">Average particle diameter [nm]</entry><entry align="center" valign="middle">Image evaluation</entry></row></thead><tbody><row><entry morerows="11" align="center" valign="middle">Example 45</entry><entry morerows="2" align="center" valign="middle">Si-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/Ar</entry><entry align="center" valign="middle">2.E+10</entry><entry align="center" valign="middle">0.6</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">9.E+09</entry><entry align="center" valign="middle">2</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">5.E+04</entry><entry align="center" valign="middle">17</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Mg-N</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub></entry><entry align="center" valign="middle">1.E+11</entry><entry align="center" valign="middle">0.5</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">4.E+11</entry><entry align="center" valign="middle">1</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">2.E+02</entry><entry align="center" valign="middle">21</entry><entry align="center" valign="middle">×</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Mg-O</entry><entry morerows="2" align="center" valign="middle">O<sub>2</sub></entry><entry align="center" valign="middle">1.E+14<<</entry><entry align="center" valign="middle">0.4</entry><entry align="center" valign="middle">×</entry></row><row><entry align="center" valign="middle">9.E+08</entry><entry align="center" valign="middle">8</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">9.E+07</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry morerows="2" align="center" valign="middle">Si-Mg-N-O</entry><entry morerows="2" align="center" valign="middle">N<sub>2</sub>/O<sub>2</sub></entry><entry align="center" valign="middle">6.E+06</entry><entry align="center" valign="middle">9</entry><entry align="center" valign="middle">⊚</entry></row><row><entry align="center" valign="middle">1.E+04</entry><entry align="center" valign="middle">10</entry><entry align="center" valign="middle">○</entry></row><row><entry align="center" valign="middle">1.E+00</entry><entry align="center" valign="middle">24</entry><entry align="center" valign="middle">×</entry></row></tbody></tgroup></table></tables>
0366As described above, the present invention can provide the resistive film which is superior controllability for a resistivity value, stability and reproducibility, has adequate temperature characteristics of resistance, and is suitable for an antistatic film.
0367In addition, the present invention can provide a picture display unit having the effect of reducing the instability of a display image, which originates from a temperature distribution in an airtight vessel caused by a temperature difference between a pair of substrates that compose the airtight vessel, and having superior display performance.
0368An antistatic film installed in an airtight vessel containing an electron source of an electron-generating device such as a picture display unit has a structure comprising an image of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride; and thereby improves controllability for a resistivity value, stability and reproducibility, and the adequate temperature characteristics of resistance.
0369This application is a divisional application of European patent application no. <patcit id="pcit0004" dnum="EP05001204A"><text>05 001 204.6</text></patcit> (the "parent application"), also published under no. <patcit id="pcit0005" dnum="EP1557863A"><text>EP 1557863</text></patcit>. The original claims of the parent application are repeated below in the present specification and form part of the content of this divisional application as filed. <ol id="ol0001" ol-style=""><li>1. An antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.</li><li>2. An antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.</li><li>3. An antistatic film having a structure comprising a plurality of conductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.</li><li>4. The antistatic film according to claim 1, wherein the conductor particle is a platinum particle, and the nitride is aluminum nitride.</li><li>5. The antistatic film according to claim 2, wherein the conductor particle is a platinum particle, and the oxide is aluminum oxide.</li><li>6. The antistatic film according to claim 3, wherein the conductor particle is a platinum particle, the nitride is aluminum nitride, and the oxide is aluminum oxide.</li><li>7. An antistatic film according to claim 1, wherein the conductor particle is a gold particle, and the nitride is aluminum nitride.</li><li>8. An antistatic film according to claim 2, wherein the conductor particle is a gold particle, and the oxide is aluminum oxide.</li><li>9. An antistatic film according to claim 3, wherein the conductor particle is a gold particle, the nitride is aluminum nitride, and the oxide is aluminum oxide.</li><li>10. The antistatic film according to claim 1, wherein the conductor particle is a silver particle, and the nitride is aluminum nitride.</li><li>11. The antistatic film according to claim 2, wherein the conductor particle is a silver particle, and the oxide is aluminum oxide.</li><li>12. The antistatic film according to claim 3, wherein the conductor particle is a silver particle, the nitride is aluminum nitride, and the oxide is aluminum oxide.</li><li>13. The antistatic film according to any one of claims 1 to 12, wherein the content of the conductor is 0.1 to 10 atomic%.</li><li>14. An antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride.</li><li>15. An antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing an oxide.</li><li>16. An antistatic film having a structure comprising a plurality of semiconductor particles with particle diameters of 0.5 to 10 nm dispersed in a medium containing a nitride and an oxide.</li><li>17. The antistatic film according to claim 14, wherein the semiconductor particle is a germanium particle, and the nitride is silicon nitride.</li><li>18. The antistatic film according to claim 15, wherein the semiconductor particle is a germanium particle, and the oxide is silicon oxide.</li><li>19. The antistatic film according to claim 16, wherein the semiconductor particle is a germanium particle, the nitride is silicon nitride, and the oxide is silicon oxide.</li><li>20. The antistatic film according to any one of claims 14 to 19, wherein the content of the semiconductor is 0.1 to 10 atomic%.</li><li>21. The antistatic film according to any one of claims 1 to 20, wherein the particle diameter is 1.0 to 9.0 nm.</li><li>22. The antistatic film according to any one of claims 1 to 21, wherein the resistivity is p = 1×10<sup>4</sup> to 1×10<sup>11</sup> Ω cm.</li><li>23. An electron-generating device with an electron source in an airtight vessel, comprising the antistatic film according to any one of claims 1 to 22, in the airtight vessel.</li><li>24. A picture display unit provided with an airtight vessel having a first substrate with an electron source arranged thereon, and a second substrate with an image display member arranged thereon so as to face the electron source, and a spacer arranged between the first and second substrates in the airtight vessel, wherein the spacer has the antistatic film according to any one of claims 1 to 22, arranged on the surface.</li><li>25. A spacer arranged between a first substrate and a second substrate in a picture display unit provided with an airtight vessel having the first substrate with an electron source arranged thereon and the second substrate having an image display member arranged thereon so as to face the electron source, wherein the spacer has the antistatic film according to any one of claims 1 to 22 on the surface.</li><li>26. A mixture target of aluminum and platinum including 95 wt.% or more aluminum and platinum, which is used for forming an antistatic film containing aluminum and platinum by a sputtering technique.</li><li>27. A mixture target of aluminum nitride and platinum including 95 wt.% or more aluminum and platinum, which is used for forming an antistatic film containing aluminum and platinum by a sputtering technique.</li><li>28. A method for manufacturing an antistatic film containing aluminum and platinum, comprising sputtering the mixture target according to claim 26 or 27 in an atmosphere containing only nitrogen.</li><li>29. A method for manufacturing an antistatic film containing aluminum and platinum, comprising sputtering the mixture target according to claim 26 in an atmosphere containing only oxygen.</li><li>30. A method for manufacturing an antistatic film containing aluminum and platinum, comprising sputtering the mixture target according to claim 26 in an atmosphere containing nitrogen and oxygen.</li><li>31. A mixture target of aluminum and gold including 95 wt.% or more aluminum and gold, which is used for forming an antistatic film containing aluminum and gold by a sputtering technique.</li><li>32. A mixture target of aluminum nitride and gold including 95 wt.% or more aluminum and gold, which is used for forming an antistatic film containing aluminum and gold by a sputtering technique.</li><li>33. A method for manufacturing an antistatic film containing aluminum and gold, comprising sputtering the mixture target according to claim 31 or 32 in an atmosphere containing only nitrogen.</li><li>34. A method for manufacturing an antistatic film containing aluminum and gold, comprising sputtering the mixture target according to claim 31 in an atmosphere containing only oxygen.</li><li>35. A method for manufacturing an antistatic film containing aluminum and gold, comprising sputtering the mixture target according to claim 31 in an atmosphere containing nitrogen and oxygen.</li><li>36. A mixture target of aluminum and silver including 95 wt.% or more aluminum and silver, which is used for forming an antistatic film containing aluminum and silver by a sputtering technique.</li><li>37. A mixture target of aluminum nitride and silver including 95 wt.% or more aluminum and silver, which is used for forming an antistatic film containing aluminum and silver by a sputtering technique.</li><li>38. A method for manufacturing an antistatic film containing aluminum and silver, comprising sputtering the mixture target according to claim 36 or 37 in an atmosphere containing only nitrogen.</li><li>39. A method for manufacturing an antistatic film containing aluminum and silver, comprising sputtering the mixture target according to claim 36 in an atmosphere containing only oxygen.</li><li>40. A method for manufacturing an antistatic film containing aluminum and silver, comprising sputtering the mixture target according to claim 36 in an atmosphere containing nitrogen and oxygen.</li></ol>
Contents4
12 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| WO2013082080A1 | Cited by | World Intellectual Property Organization (WIPO) | International search |
| US8957394B2 | Cited by | United States of America | Applicant |
| EP0991102A1 | Cites | European Patent Office (EPO) | Applicant |
| EP1203788A1 | Cites | European Patent Office (EPO) | Applicant |
| JPH10284283A | Cites | Japan | Search report |
| JPH10284285A | Cites | Japan | Search report |
| JPH10284286A | Cites | Japan | Search report |
20 members in 5 offices
Priority claims7
| Document | Office | Kind | Date |
|---|---|---|---|
| 2004014469 | Japan | A | |
| 2004014469 | Japan | – | |
| 05001204 | European Patent Office (EPO) | A | |
| EP20050001204 | – | – | – |
| JP20040014469 | – | – | – |
| 05001204 | – | – | – |
| 2004014469 | – | – | – |
Members20
| Document | Office | Kind | |
|---|---|---|---|
| EP1557863A2 | European Patent Office (EPO) | A2 | |
| KR20050076757A | Republic of Korea | A | |
| JP2005235751A | Japan | A | |
| CN1668162A | China | A | |
| US2005227062A1 | United States of America | A1 | |
| KR20060131702A | Republic of Korea | A | |
| JP2006344603A | Japan | A | |
| KR100744334B1 | Republic of Korea | B1 | |
| KR20070089768A | Republic of Korea | A | |
| EP1557863A3 | European Patent Office (EPO) | A3 | |
| KR100781001B1 | Republic of Korea | B1 | |
| JP4027373B2 | Japan | B2 | |
| CN101220459A | China | A | |
| KR100847410B1 | Republic of Korea | B1 | |
| EP1998355A2This record | European Patent Office (EPO) | A2 | |
| CN101340770A | China | A | |
| EP1998355A3 | European Patent Office (EPO) | A3 | |
| JP4448109B2 | Japan | B2 | |
| US8004173B2 | United States of America | B2 | |
| EP1557863B1 | European Patent Office (EPO) | B1 |
10 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Application withdrawnWithdrawn18W | 18W | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: THE APPLICATION HAS BEEN WITHDRAWNSTAA | STAA | |
| First examination report despatched17Q | 17Q | |
| Request for examination filed17P | 17P | |
| Designation fees paidAKX | AKX | |
| Designated contracting statesAK | AK | |
| Search report despatchedORIGINAL CODE: 0009013PUAL | PUAL | |
| Divisional application: reference to earlier applicationAC | AC | |
| Designated contracting statesAK | AK | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI |
Numbers
- Publication
- 1998355
- Publication, DOCDB
- 1998355
- Publication, EPODOC
- EP1998355
- Application
- 8162367
- Application, DOCDB
- 08162367
- Application, EPODOC
- EP20080162367
Titles3
- German
- Antistatische Folie, Distanzstück damit und Bildanzeigeeinheit
- English
- Antistatic film, spacer using it and picture display unit
- French
- Film antistatique, espaceur l'utilisant et unité d'affichage d'images
Classification
- CPC, 11
- C23C14/3414
- C09K3/16
- C23C14/0036
- C23C14/0688
- H01J9/242
- H01J29/028
- H01J29/864
- H01J2329/864
- H01J2329/8645
- H01J2329/8655
- Y10T428/25
- IPC, 9
- H01J31 02
- H01J31 12
- C09K3 16
- C23C14 00
- C23C14 06
- C23C14 34
- H01J9 24
- H01J29 02
- H01J29 86
Designated states5
- Contracting states, 5
- Germany
- France
- United Kingdom
- Italy
- Netherlands (Kingdom of the)