Sputtered titanium oxynitride films

[Detailed Description of the Invention]

The present invention relates to the art which carries out sputtering of the metal content film on a nonmetallic substrate, and, more particularly, generally relates to the art which carries out sputtering of the multilayer metal dielectric transparent membrane to glass. In U.S. Pat. No. 3990784 of Gelber, The structural covering glass system containing a transparent substrate and the multilayer coat which has a dielectric layer between the 1st and 2nd metal layers is indicated, and it is a ratio of the thickness of the 1st and 2nd metal layers, The transparent rate of a tunic is made to change regardless of that reflective characteristic by changing the thickness of each metal layer, maintaining this ratio uniformly. The reflection from a tunic seems not to color the thickness of a dielectric layer deeply. In U.S. Pat. No. 4022947 of Grubb and others, While reflecting most incidence sunlight, the method of carrying out sputtering of iron, nickel, or the chromium alloy, obtaining a transparent metal membrane, in order to manufacture the transparent panel and it which may make the visible light of a request rate penetrate, carrying out sputtering of the same thing or the same alloy in reaction under existence of oxygen, and obtaining an oxide film is indicated. In 1 suitable mode, a metal membrane exists between a substrate and a metal oxide film. In another suitable mode, a metal oxide film exists between a substrate and a metal membrane. In U.S. Pat. No. 4534841 of Hartig and others, it is optical 20~280 m in thickness to a transparent substrate by the negative pole evaporating method.^-9Of an oxide layer is covered first and, subsequently it is geometric 10~40 m in thickness.^-9The solar control panel glass manufactured by covering a Nitriding chromium layer is indicated. The optical 3rd dielectric layer may be covered to the 2nd layer. An oxide layer is chosen from each oxide of tin, titanium, and aluminum. In U.S. Pat. No. 4535000 of Gordon, Providing the thin film of metal nitride, for example, titanium nitride, in a glass board material is indicated by mixing halogenated metal with reducing gas like ammonia by 250~230 degreeC, making this gas react in the glass surface heated by 400~700 degreeC, and forming a film on glass. The sheet glass which has a multilayer tunic chosen as U.S. Pat. No. 4546050 from Amberger from the group which comprises copper, stainless steel, titanium dioxide; copper, titanium, and titanium dioxide;, copper, titanium, and titanium nitride is indicated. The structural glassware which has a film of metal and/or a metal oxide is increasing importance as the energy which heating and air conditioning take becomes increasingly expensive. Generally structural covering glassware is classified into two. That is, they are an object for solar-heat control, and covering a high penetration / product for low radiation. Generally as for the product for solar-heat control, the low visible light passage coloring film is covered by the glass board material of light coloring, and this film reduces the penetration of the solar heat from a window to the inside of a building, and is reducing air-conditioning cost. Most [ it is very effective and ] this product as a commercial structure is seen in a warm zone. Especially in the area where heating cost poses a big problem, in the building for dwellings, the transmissivity of the visible light to an inside is improved, and on the other hand, in order to reflect infrared rays and to hold heat inside a building, the high penetration / a low radiation tunic is desired. A high penetration / low radiation tunic is multilayer films typically, and Infrared reflective metal is inserted [ copper / silver, gold, and / when ] between Anti-reflection metal oxide layers when with the oxide of bismuth, indium, and/or tin. On the other hand, a solar-heat control film is a single layer film which consists of one sort of metal, such as cobalt, iron, chromium, nickel, and copper, or a metal oxide, or two sorts or more typically. The wet process for manufacturing the metal membrane for solar-heat control is publicly known from U.S. Pat. No. 3846152, No. 4091172, No. 3723158, and No. 3457138. The thermal decomposition method for manufacturing the metal oxide film for solar-heat control is publicly known from U.S. Pat. No. 3660061, No. 3658568, No. 3978272, and No. 4100330. The sputtering art for manufacturing a high penetration / low radiation multilayer tunic is indicated by U.S. Pat. No. 4462884 and No. 4508789. It is indicated by U.S. Pat. No. 4512863 and No. 4594137 with the sputtering art for manufacturing a solar-heat control film. The abstract of an invention The present invention provides the dielectric film which is used for the multilayer structural tunic of the varieties on glass and which was new and excellent. The present invention is Oxy titanium nitride "Ti._xN_yO_z: Although x, y, and z are relative rates, in order to make a tunic including that it is not fixed" adhere, start carrying out sputtering considering titanium as the negative pole within the atmosphere containing oxygen and nitrogen. The Oxy titanium nitride film of the present invention is made to adhere in combination with a Infrared reflection film with silver when, and can form a multilayer low radiation film. The Oxy titanium nitride film of the present invention is made to adhere in combination with a Alloy film with stainless steel or the Inconel alloy when, and can form the coloring multilayer tunic which carried out the comparatively vivid color. The Oxy titanium nitride film of the present invention is made to adhere in combination with a Alloy film again with silver, the metal membrane to which a Infrared reflection film and the rate of a light reflex are reduced when, especially the Inconel alloy when, and can form the multilayer tunic of a low radiation rate of a comparatively vivid color. Detailed explanation of a suitable mode The product containing the Oxy titanium nitride which a transparent nonmetallic substrate, preferably glass are covered with negative pole sputtering, preferably magnetron sputtering, and has desired endurance and aesthetic characteristic is given. In the conventional magnetron sputtering method, a substrate goes with the target side of the material by which sputtering should be carried out, and is placed on the interior of a room for Fitted together covering. The plastic which is not damaged according to the operation conditions of glass, ceramics, and a covering process as a suitable substrate by the present invention is mentioned. Then is good at a conventional design, preferably a rectangular design, it is connected to a power supply, and the negative pole is preferably used in combination with a magnetic field, and raises sputtering processing. At least one negative pole target side contains the titanium which sputtering is carried out within a reactant atmosphere and forms a Oxy nitriding film. Assembly object of the anode which is indicated by U.S. Pat. No. 4478702 of Gillery and others and which was designed symmetrically and positioned is preferred. It adheres to the Oxy titanium nitride film of the present invention by making titanium into the negative pole and carrying out sputtering within the atmosphere containing oxygen and nitrogen. Composition of this atmosphere is the range of 10~50% of oxygen, and the range of 90~50% of nitrogen preferably. Especially the atmosphere whose 10~25% of oxygen and remainder are nitrogen is preferred. The drawing shows that the character of Oxy titanium nitride changes gradually and continuously, if gas composition changes. The titanium by which sputtering was carried out within oxygen/argon atmosphere changes from an oxide to metal rapidly in contrast with this. It is shown that the drawing can choose adhesion conditions so that sputtering can be further carried out at the rate of a request of the Oxy titanium nitride film which has a desired penetration and the characteristic of absorption. The tunic color of a certain request can be manufactured as an object for construction combining the coloring metal layer of a colorless dielectric material, an inner side, and the outside, or by combining a coloring metal oxide and reflective metal. the present invention -- therefore, a desired tunic color is obtained by obtaining the very vivid dark color of low radioactivity combining Oxy titanium nitride and high infrared reflective metal, such as silver. The rate of a light reflex can be reduced by using Neutral metal if needed when with each alloy of nickel and iron especially the Inconel alloy, and stainless steel without sacrificing the purity or the radiation rate of a color, when the rate of a light reflex of such a tunic is higher than a request. The present invention enables manufacture of a series of coloring tunics using the minimum number of layers and material. The tunic system of the present invention has chroma saturation with low reflection and a comparatively high color, and one endurance. It is known that a series of colors can be made by providing the 1st and 2nd metal layers in the upper and lower sides of the layer of transparent dielectric material. If the color changes the thickness of a dielectric layer, it will change. however, the dielectric used conventionally -- quick sputtering and a high refractive index and good endurance -- when -- the It was required characteristic -- with, it was not. The Oxy titanium nitride of the present invention can obtain the structural tunic of a dark color by having these characteristics and combining with a suitable metal membrane. For example, it can use for the combination of Oxy titanium nitride and a nickel alloy taking out the attractive color which was excellent in endurance. The two-layer combination of metal and a dielectric is determined that it will have the optimal thickness of each class which gives the combination of the minimum reflectance and the highest degree of color using a reflective circular figure and computer calculation. The transmissivity of the tunic of the optimal thickness is so low that the refractive index of a dielectric is high, and the chroma saturation of a color becomes high. the metal which has low n and high k (n and k are the real parts and imaginary parts of a complex index of refraction here -- the electromagnetism within a medium -- propagation of a line is specified) has the tendency to give the minimum transmissivity and the highest chroma saturation. If metaled thickness is increased in order to reduce transmissivity, reflectance will increase and it will become a light color. If an ultra-thin metal layer is made to adhere before adhesion of a dielectric layer, reflectance can be reduced and a clearer color can be obtained. If the increase of the thickness of the main metal layer and an ultra-thin metal layer are combined, the tunic of a low penetration, low reflection, and the Takagi color can be obtained. When using the two main metal layers, the most attractive appearance will be given if a low refractive-index dielectric is combined with the metal of low n and high k. According to calculation, if metal is used in combination with the dielectric of refractive index 2.3 in the case of 20% of transmissivity, suitable chroma saturation can be obtained. In the case of transmissivity lower than this, the system of metal-dielectric-metal is preferred. In the case of the Oxy titanium nitride of the present invention, the multilayer tunic which has good character using much metal or the film of an alloy can be obtained. Alloy is mentioned [ titanium / when ] when with Metal, a nickel alloy, and an iron alloy as a suitable film. Chemical resistance is high, and it is neutrality to a color, and since adhesion is easy, a nickel alloy is preferred. It is a pure glass board material preferably 10^-4Less than Toru, more preferably 2x10^-5It puts on the interior of a room for covering exhausted at less than Toru. It is a selected atmosphere of reactant gas preferably nitrogen, and oxygen About 5x10^-4Toru and 10^-2It builds with the pressure between Torus indoors. The negative pole which has a target side of titanium is operated to the whole surface of the substrate which should be covered. Carry out sputtering of the target metal, it is made to react to an indoor atmosphere, and a Oxy titanium nitride tunic layer is made to adhere on a glass surface. After making the layer of the beginning of Oxy titanium nitride adhere, the room for covering is exhausted, and it is [ pure argon and ] Inert atmosphere when About 5x10^-4Toru and 10^-2It builds with the pressure between Torus. The negative pole which has a target side of metal or an alloy is operated to the whole Oxy titanium nitride covering side. Sputtering of the target is carried out and sputtering of the metal layer is carried out to a Oxy titanium nitride covering glass surface. A suitable metal is titanium. It is preferred for the Inconel alloy, a nickel alloy, stainless steel, and an iron alloy to be mentioned as a suitable alloy, and to carry out sputtering by 4~6-mtorr pressure in pure argon. A metal membrane is made to adhere to the upper row of a Oxy titanium nitride film downward in the suitable mode of the present invention. Most dominant wavelength of the color reflected from a non-coated side is altogether dependent on the thickness of a Oxy titanium nitride layer like [ in the case of two layer membranes ]. The thickness of a surface metal layer is changed until transmissivity reaches a request value mostly, and subsequently, the thickness of a lower layer metal layer is changed until the reflectance of the request from the non-coated side of an article is attained. It may sometimes be required for the final adjustment of the thickness of a surface metal membrane to obtain the optimal last transmissivity. If the thickness of a surface metal membrane is increased to related thickness within the limits, transmissivity will fall and the reflectance from the non-coated side of a covering article will increase. If the thickness of the metal membrane of the bottom of the heap is increased, transmissivity will increase and the reflectance from a non-coated side will fall. In the suitable mode of the present invention, negative pole sputtering adheres to a multilayer film, and it forms the tunic of high transmissivity and a low radiation rate. In addition to a titanium target, other at least one negative pole target side contains the metal for sputtering which forms an infrared reflective metal layer. The multilayer tunic which has an infrared reflective metal layer in combination with an antireflection Oxy titanium nitride layer is manufactured as follows. It is a pure glass board material preferably 10^-4Less than Toru, more preferably 2x10^-5It puts on the interior of a room for covering exhausted at less than Toru. It is a selected atmosphere of reactant gas preferably nitrogen, and oxygen About 5x10^-4Toru and 10^-2It builds with the pressure between Torus indoors. The negative pole which has a target side of titanium is preferably operated on the electric power level of 5~10 kW to the whole surface of the substrate which should be covered. Carry out sputtering of the target metal, it is made to react to an indoor atmosphere, and a Oxy titanium nitride tunic layer is made to adhere on a glass surface. After making the layer of the beginning of Oxy titanium nitride adhere, the room for covering is exhausted, and it is [ pure argon and ] Inert atmosphere when About 5x10^-4Toru and 10^-2It builds with the pressure between Torus. The negative pole which has a silver target side is operated to the whole Oxy titanium nitride covering side. Sputtering of the target metal is carried out and the conductive metal layer whose infrared reflectance it is uniform to a Oxy titanium nitride covering glass surface, and is high is made to adhere. The 2nd layer of Oxy titanium nitride is made to adhere to a silver larer on the essentially same conditions as having used for adhesion of the 1st Oxy titanium nitride layer. The present invention will further be understood by explanation of the following examples. Example 1 10-kW electric power was supplied in the decompression chamber which has the atmosphere of 23% of oxygen, and 77% of nitrogen by pressure the torr of 4 mm at a titanium negative pole target with a size of 5x17 inches (about 12.7x43.2 cm). The negative pole is fixed and a glass board material passes the lower part of a sputtering target side the speed for 120 inch (about 3 m)/. The film containing Oxy titanium nitride adheres to a glass surface in four passage, and they are transmissivity 75.7 and Noodle. Example 2 The 1st layer that contains Oxy titanium nitride in a glass board material like the case of Example 1 was covered. Subsequently, the uniform silver larer was covered with the sputtering of the silver negative pole target energized by 0.27 kW in pressure torr of the argon atmosphere of 4 mm to the Oxy titanium nitride covering side, and, finally transmissivity was made into 68% in it. In order to protect silver from oxidization, passed once the titanium negative pole to which 0.03 kW was supplied in 4-mtorr argon, the ultra-thin protective coating of titanium was made to adhere, and the last transmissivity was made into 67.5%. Example 3 To the glass board material, Oxy titanium nitride and silver were covered like each above-mentioned example. Ivy which makes the 2nd layer of Oxy titanium nitride adhere, makes the last transmissivity 82.1%, and attaches the covering article of high transmissivity and a low radiation rate after making the thin protection layer of titanium adhere. Example 4 Electric power (645 v and 10 kW) was supplied in the decompression chamber which has the atmosphere of 23% of oxygen, and 77% of nitrogen by pressure the torr of 4 mm at a titanium negative pole target with a size of 5x17 inches (about 12.7x43.2 cm). The negative pole was made to pass a glass board material once the speed for 108 inch (about 2.74 m)/, and Oxy titanium nitride was covered. A room was exhausted and the atmosphere of pure argon was introduced by 4-mtorr pressure. 2.5 A and 441 v were supplied to the silver negative pole, and sputtering of the silver film was carried out once to the Oxy titanium nitride covering side by passage by a part for 120 inch (about 3.05 m)/. In order to protect a silver film from oxidization, the ultra-thin layer of the nickel alloy was made to adhere on silver. The remainder supplied 1 A and 352 v to the target of Inconel 625 which consists of nickel Molydeven 9% 3% of iron, and niobium 4% chromium 18.6%. Sputtering of the nickel alloy was carried out in 4-mtorr pure argon, and the substrate was passed once by a part for 120 inch (about 3.05 m)/. Optical transmittance is 54.6% and a covering article is [ the reflectance from a 21.3% side and a non-coated side ] Oh. The color which the color coordinates from a non-coated side are x= 0.3516 and y= 0.3805, and was observed is light yellow, and Oh. Example 5 It should fully reflect combining the Oxy titanium nitride film and the silver film, and should resemble the gold film in the intermediary and appearance which attach yellow deep enough. Sputtering was carried out like Example 4 except having lessened oxygen of 4-mtorr atmosphere by making into the negative pole the titanium to which 640 v and 10 kW were supplied. It was made to pass once by a part for 120 inch (about 3.05 m)/in the atmosphere for which oxygen was slightly insufficient, and the Oxy titanium nitride film whose absorbency is a little larger than the Oxy titanium nitride film of Example 4 was obtained. Sputtering of the silver negative pole to which 2.4 A and 441 v were supplied was carried out in 4-mtorr pure argon, and the silver film was made to adhere to a Oxy titanium nitride covering side by passage once in a part for 120 inch (about 3.05 m)/. In order to protect a silver film from oxidization, sputtering of the ultra-thin film of the same nickel alloy as the case of Example 4 was carried out in 4-mtorr argon by the 1-time passage for 120 inch (3.05 m)/with the negative pole target of Inconel 625 metal to which 1 A and 356 v were supplied. The optical transmittance of a covering article is almost the same as the article of Example 4, Oh of the reflectance from a non-coated side is 40.2%, color coordinates are x= 0.3833 and y= 0.4093, and it is Oh. It is golden, and is a dark color from the color of Example 4, and the observed color is Oh. This film did not produce cloudy weather to the cold heat examination. Example 6 The multilayer tunic of Oxy titanium nitride and a nickel alloy was made to adhere to a glass board material on the following conditions. The pure glass board material was placed by pressure the torr of 6 mm in the decompression chamber of atmosphere of 15% of oxygen, and 85% of nitrogen. Eight passage is required to build the Oxy titanium nitride film of the thickness which has primary blue with 120 inches (about 3 m) of titanium negative pole /linear velocity of a part to which 6.7 kW was supplied, and it is Oh. Subsequently, the bottom of a nickel alloy target was passed for the Oxy titanium nitride covering glass surface in pure argon. Chromium 18.6%, 3% of iron, and niobium 4% and Molydeven 9% and the remainder are Inconel 625 of nickel, and the nickel alloy in this example is Oh. Thermal spraying of the nickel alloy layer was carried out to the thickness which is sufficient for reducing transmissivity to 22%. The chromaticity coordinates of this tunic are x= 0.3198 and y= 0.2863 in the reflection from a non-coated glass surface, and are Oh. The observed color is purple system pink, the rate of a light reflex from a non-coated glass surface is 5.65, and it is Oh. Example 7 Ivy which attaches the tunic which has attractive blue with about 20% of optical transmittance on the conditions shown in a The table using the same Oxy titanium nitride Inconel layer composition as the case of Example 6. The color tone paragraph of a two-layer tunic is easy. Hue is adjusted by the thickness of Oxy titanium nitride. A layer is too thick when green is too strong. A layer is too thin when red is too strong. The thickness of Oxy titanium nitride also affects transmissivity (or reflectance). This is because a reddish blue tunic has high transmissivity more generally than a green system blue tunic. However, once a pigmented layer is decided, the transmissivity (or reflectance) can change and adjust the thickness of the Inconel alloy layer. If the thickness is increased, transmissivity will fall and reflectance will increase, as expected. This change hardly affects the main wavelengths of hue. The influence which thickness change of the layer expressed as % of the tunic thickness obtained on each conditions shown in the The table has on the color of five kinds of two-layer tunics of this example was shown in the The table.

[Table]

[Table]

Example 8 Sputtering covering of the 1st layer of the Inconel alloy 625 was carried out so that optical transmittance might be 60% to a glass board material like each above-mentioned example. Sputtering of the Oxy titanium nitride film was carried out on the nickel alloy like each above-mentioned example. Sputtering of the 2nd nickel alloy film was carried out so that the last optical transmittance might be 22%. From a glass table, the chromaticity coordinates of a tunic are x= 0.2644 and y= 0.2340, and are Oh. The observed color is purple, the rate of a light reflex from a non-coated glass surface is 8.9%, and it is Oh. Example 9 Ivy which changes each thickness of a Oxy titanium nitride layer and the Inconel layer, and attaches a series of three-layer tunics. The result about these samples was shown in the The table. In the The table, thickness was expressed as % of the thickness obtained in the The table using the conditions of a statement.

[Table]

[Table]

[Table]

Example 10 The Oxy titanium nitride film was made to adhere to a glass board material side like Example 6. The stainless steel film was made to adhere all over this Oxy titanium nitride. From a glass surface, the chromaticity coordinates of this tunic are x= 0.2466 and y= 0.2680, and are Oh. The observed color is green system blue, the rate of a light reflex from a non-coated glass surface is 18.5%, and it is Oh. Example 11 The Oxy titanium nitride film was made to adhere to a glass surface by passage 8 times like each above-mentioned example. In argon, titanium was made into the negative pole, sputtering was carried out, and the titanium metal membrane was made to adhere. The chromaticity coordinates from the glass of a tunic are x= 0.3317 and y= 0.3037, and are Oh. The observed color is purple system pink, the rate of a light reflex from a non-coated glass surface is 5.17%, and it is Oh. Example 12 The Oxy titanium nitride film was made to adhere to a glass surface by passage 9 times like Example 11. In argon, titanium was made into the negative pole, sputtering was carried out, and the titanium metal membrane was made to adhere. The chromaticity coordinates from the glass surface of a tunic are x= 0.2402 and y= 0.2265, and are Oh. The observed color is purple system blue, the rate of a light reflex from a non-coated glass surface is 5.32%, and it is Oh. Each above example is shown in order to explain the advantage of the present invention. The tunic shown in the The table and the The table was not invaded by the 20% chloride of room temperature, or 30% nitric acid of room temperature during 24 hours. By the 275= (135degreeC) heating test for 5 hours, a change slight to transmissivity and a change slight in a reflective color are Oh. This is in agreement with growth of the protective oxide on Inconel which is a process considered to be also finite. In the Cleveland condensation high humidity test in 150= (about 66degreeC), change of the tunic was not accepted in four months. The tunic was not repeatedly affected to the scratch by the eraser used for evaluating the internal one crazing of a tunic at a bristly hair brush examination. However, when it rubs with humidity or a dry pumice stone, as for a tunic, it is I and It was that it is not so hard as a titanium nitride film. There are not many attractive products which can be manufactured by the combination layer of Oxy titanium nitride / alloy. However, by metal / Oxy titanium nitride / metal system, wide range reflected colors and transmissivity can be far obtained using only two kinds of materials. the same grade as each oxide of tin or zinc which Oxy titanium nitride is transparent, is chemical resistance, has a high refractive index, and is inferior in character -- it adheres quickly. Unless adhesion speed is increased to the absolute peak price, the concentration of oxygen in nitrogen is not so important as can be considered for the method of the present invention. For this reason, the complexity of the monitor in a device which cannot distinguish decline in the transmissivity by the increase in film thickness and decline in the transmissivity by the increase in absorption that it is only reliable only in transmissivity mode is lost. Therefore, color control of a two-layer tunic is not difficult. About a three-layer tunic, it becomes a little complicated [ color control ], for example, when reflectance is too high, the complexity of color control decreases by making a surface metal layer thin or thickening the lowest metal layer. Each above-mentioned example is shown in order to explain the present invention. Various sputtering conditions can be used, the ratio of oxygen and nitrogen can be changed, and wide range reflected colors can be obtained, using the Oxy titanium nitride film of the present invention together with the metal content film of others [ various thickness and composition ]. The range of the present invention is prescribed by the claim.

[Brief Description of the Drawings]

Transmissivity [ in / in Drawing 1 / 550 nm of the Oxy titanium nitride film on glass ], The figure shown as a function of the film thickness measured by the number of times of negative pole passage in oxygen of various % in nitrogen, Drawing 2 is the adhesion speed (unit A) of the Oxy titanium nitride per negative pole passage, the figure shown as a function of % of oxygen within the atmosphere of the room for covering, and Drawing 3 -- about [ thickness ] -- the figure showing absorption of the Oxy titanium nitride film of 600A as a function of % of oxygen within the atmosphere of the room for covering, Drawing 4 is a figure showing the transmissivity at 550 nm of the Oxy titanium nitride film on the Inconel alloy film as a function of the film thickness in various electric power levels of the negative pole.