Material of chemical compounds with a metal in group iv a of the periodic system, nitrogen and oxygen and process for producing it

Description: TECHNICAL FIELD [Detailed description of the invention] Technical field of invention The present invention relates to the substance according to claim 1, the method for using the substance according to claim 17, 21 or 23, and the method for producing the substance according to claim 24. Background of the invention Compounds of titanium and nitrogen and oxygen cover a wide range of known properties of substances and are therefore widely used in industry. Titanium dioxide is, for example, the main component of wall paint, but is also used as a solar cell. The compound TiN is known as a conductive ceramic and is distinguished by its high resistance and hardness. The tool is thereby increased in hardness, and this compound is used in the semiconductor industry as a diffusion barrier between silicon and aluminum. Mixtures of TiN and titanium oxide phases have not been well studied. As a practical application, a material that combines the two properties of a dielectric and a metal would be very attractive. German Published Patent No. 3,522,427 The author of A1 discloses materials containing titanium and nitrogen whose electrical properties have been adapted to various applications by mixing with oxygen. This results in changes in the chemical composition and has a negative effect on other physical and chemical properties such as adhesion, corrosion resistance, temperature resistance or hardness. A particular disadvantage is the fact that this substance tends to oxidize when exposed to oxygen. However, since the desired properties are determined by the proportion of oxygen, they vary over time, depending on the method of practical use. Blickensderfer, et al., U.S. Pat. No. 4,098,956 discloses a selective absorbent, which is TiN._xO_yIt is covered with. The patentee reports on the presence of oxygen and carbon in the coating. As a decisive feature, the patentee does not state or know that voids or spaces are essential properties for application. The US patent has the drawback that its optical properties can only meet various requirements by changing the chemical composition. Changes in the chemical composition cause the loss of other required properties, such as adhesion. The above patentees have described these shortcomings in other publications: Blickens-derfer, R., DK Deardorff, RLLoncoln. 1997. "TiN as a selective solar absorber_xAnd ZrN_xThe spectral reflectance of the film is reported, and the problem of decomposition in the case of such materials is described. Aside from extensive research on TiN (see, eg, DE 3,210,420 or DE 3,300,694) and titanium dioxide (see, eg, DE 3,116,677), titanium oxynitride (TiN)._xO_y) Is Vogelzang, E., J.Sjollema, HJBoer, J.Th.M.DeHosson.1987. "TiN"_xO_y"Optical absorption in compounds" was studied by J. Appl. Phys. 61 (9): 4606-4611). In the cited study, the complex permittivity e (λ) as a function of the wavelength λ in the range 0.4-30 μm was published along with other measurements. If those published values and Fresnel theory are used to calculate the degree of reflectance and transmittance, the calculated values are with the published results of the authors doing the same study. Will not match. Therefore, it must be assumed that errors are infiltrating in the determination of e (λ). Therefore, the explanation of optical and dielectric behavior in this study is similarly inadequate and practical application is not possible for that reason. In German Publication No. 3,640,086 A1, compounds of titanium, nitrogen, oxygen and carbon were published. It is required to have a higher proportion of oxygen than nitrogen or carbon. However, in this case, the proportion of voids is not considered. German Publication Patent No. 3,637,810 for the production of substances containing titanium, nitrogen and carbon It is disclosed in A1. It is known that a dense layer is expressed by using ion plating. Therefore, it is taken as a starting point that there are no voids in those layers. Substances with voids (or spaces) are rather often described in the literature, for example, thin layers consisting only of TiN (eg Martin, PJ, RPNetterfield and WG Sainty. 1982. "Reactive Deposition and Reactive Ion-Beam Sputtering". Manufactured by TiN_xOptical properties of "Vacuum 32: 359-362" or German Publication No. 4,207,368 A1), especially TiN_xO_yAbout Schel-linger, HMLazarov, H.Klank, R.Sizmann.1993.TiN_xO_y-Thermal and chemical metal dielectric transition of Cu absorber tandem "Proc. SPIE 2017, Optical Materials Technology for Energy Efficiency and Solar Energy Conversion XII). All authors therefore report very little about the mere existence of voids. Quantification of voids has not yet been achieved. Patent specification DT 2,216,432 C3 contains a report on titanium dioxide with open voids. The voids (stomata) reported there have a very large volume. The optical and electrical properties of a substance can be classified into dielectric and metallic properties, and the use of the substance depends on this property. In many applications, however, a mixture of the two properties is required. Absorber-Reflector Tandam (eg DE 2,639,388 C2 or DE 2,734,544) In (see C2), neither pure metal nor dielectric can selectively absorb sunlight. Doped or undoped semiconductors partially meet their requirements and are used in many applications. If one intends a selective absorber, the fixed bandgap and, typically the relative flat absorption curve for semiconductors, are the exact opposite for highly selective properties. German patent application DE-OS-3522427 relates to the manufacture of conductive temperature measuring probes (probe) and elongation measuring probes (probe), in which multiple layers of titaniumoxynitride are formed. It is attached by means of reactive ion deposition or direct current or high frequency magnetron dusting. UK Publication Patent GB-A-2186294 relates to sputtering a hard black decorative material consisting of TiOCN, ZrOCN and / or HfOCN onto a watch strap or eyeglass frame. European Patent EP-A-0564709 relates to a glass substrate to which a layer system consisting of a highly reflective material layer and a low reflective material layer adheres. The former substance is composed of oxynitride of Hf, Zr, Ta, or Ti. It is carried out by adhesion sputtering of the layer system to the substrate, thereby forming a void-free layer. U.S. Pat. No. 4,861,669 relates to forming IR reflective staples on a glass substrate by sputtering hard, transparent TiON. Japanese Patent Application Laid-Open No. 57-2875 is TiN as a decorative material such as a wristwatch strip._xO_yAnd TiO_zC_xN_yIt relates to forming a wear-resistant and corrosion-resistant colored layer consisting of. Japanese Patent Application Laid-Open No. 63-125658 relates to a decorative layer in which a 0.14 μm TiON compound is applied to a part of a wristwatch. Japanese Patent Application Laid-Open No. 63-247350 discloses the formation of a decorative layer made of titanium oxynitride. Abstract of the invention An object of the present invention is therefore to provide a wide range of preferably applicable materials such as solar energy, power generation equipment industry and decorative layers used in several applications. This material exhibits properties that are neither metallic nor dielectric. Another object of the present invention is to provide a method for producing a substance of the present invention. The above problem is solved by the configuration of the present invention shown in claims 1, 17, 21, 23 and 24. Preferred specific examples are shown in other dependent claims. Detailed explanation The material according to the invention consists of compounds of one or more metals, nitrogen and oxygen from Group IV A of the Periodic Table, in which case 2 to 45%, preferably 5 to 40% of the volume, particularly preferably. 10-28% is occupied by voids (space), and the size of the voids (0.5 nm)^３~ About (100nm)^３Is in the range of. The remaining volume of this material (98-55%, preferably 95-60%) is preferably Group IV A metals, nitrogen and oxygen in the Periodic Table 1: (0.1-1.7) :( 0.1-1.7). Indicates a composition of 1: (0.25 to 1.5): (0.25 to 1.5). This substance has the formula MN_xO_yWhere "M" indicates a metal of Group IV A of the Periodic Table IV, and x or y is a value between 0.1 and 1.7. The above ratio is the number of particles or the molar ratio. Regarding the size of the voids, the latter is in the lower range, i.e. preferably (15 nm).^３It is preferable that it occurs in the following. The "remaining volume" of a substance is MN_x(X = 0.7 to 1.2), MO system (M_nO_2n-1) Magnelli phase, MO₂, M₂One or more compounds selected from N (M = metal of Group IV A of the Periodic Table), and about 0-30%, preferably 0.5-5%, carbon compounds of the metal of Group IV A of the Periodic Table. Is included. The range of important application choices is extended by their preferably ancillary contained compounds. A small amount of titanium carbide as an impurity is unobtrusive in many applications and allows for cheaper production. The chemical phase present in the material of the present invention, preferably in crystalline or amorphous form, may be useful, for example, as a diffusion barrier in the semiconductor industry in crystalline form or as a decorative layer in amorphous form. Allows a variety of application areas to cover. The metal from Group IV A of the Periodic Table IV is titanium, zirconium or hafnium or a mixture of these two or three metals, preferably titanium. In the material of the present invention, if p is the average mass density of the individual compounds that make up the material, p_mIf is the mass density of the substance containing the voids, its size pp_mThis can be further explained by the fact that / p will be in the range 0.02 to 0.5. Furthermore, the material of the present invention preferably exhibits voids in the fractal size distribution. By the void type herein, the material of the invention is clearly limited by the material due to its reduced mass density modified lattice constant and high density. The defined void portions and void distribution allow the materials of the invention to be used as standards in the study of neutron scatters. A further property of the materials of the present invention is that the real part of the index of refraction for an X-ray wavelength of 0.0709 nm is preferably in the range 0.9999984-0.9999973. The mass density of the substance of the present invention is preferably 3.7 to 4.5 g / cm.³, Preferably 3.8-4.2 g / cm³Is. Thanks to their properties, the materials of the present invention are suitable for use as a standard in the quantification of thin film densities. A further property of the materials of the present invention is that the index of refraction for wavelengths in the range of 0.5 to 4.5 μm does not exhibit typical metal behavior or typical dielectric behavior. This makes this material very suitable as a radiation energy transducer. Utilization for converting radiation energy into heat requires optical properties in the infrared, which are neither metal nor dielectric properties. Metallic properties can be described by Drude theory of free movement of electrons in metals, but dielectric properties have a hypothetical part with a very low index of refraction. In the case of the material of the present invention, plasma wavelength λ in the sense of Drude theory of free movement of electrons in metal by electron loss spectroscopy (EELS) measurement._pIndicates a peak that can be interpreted as λ_pIs in the range of 1.1 to 0.1 μm. This plasma wavelength, however, is not related to the typical metallic behavior of optical constants (described by Drude's theory of free movement of electrons in metals). The material of the present invention is preferably available in the form of powder or glass. This also allows the use of substances in the field of volume absorbents. If a mixture of titanium, zirconium or hafnium compounds is used, the range of application of the material can be extended to fields where high temperature stability is required. Zirconium or hafnium compounds exhibit higher thermal stability than titanium compounds and are more resistant in the diffusion process. The substance of the present invention can be preferably used as a thin layer in a coating film thickness in the range of 3 nm to 3 mm, preferably in the range of 10 nm to 2 mm, and very preferably in the range of 30 to 71 nm. This thin layer preferably exhibits a columnar microstructure. This allows for use in applications where the layer is porous or coarse. This thin layer made of the material of the present invention has a resistivity (specific resistance) in the range of 30 to 30,000 μΩ · cm, preferably 100 to 6,000 μΩ · cm, and very preferably 2,000 to 3,000 μΩ · cm. This property is expected to be applied to the semiconductor industry, and if different resistivitys are required, it will be easily possible to change to a manufacturing method that meets those requirements while reducing the manufacturing cost. .. The resistivity can be adjusted without difficulty by selecting the void portion. Adopting the resistivity of a void-free material as a starting point, this property increases with the addition of voids. For example, TiN_0.98O_0.2In the case of, the resistivity is in the range of 70 μΩ · cm if the void occupies 3%, and increases to the range of 650 μΩ if the void occupies 40%. If yet other co-compounds, as described in claims 2 and 3, are present in the material, they need not be found in the same proportion at each level of the thin layer. .. This enables the use of gradient coating, for example, in the case of selective coating, it is desired to change the optical characteristics with the film thickness. This can be easily achieved by partial change of the compound or by changing the proportion of voids. Depending on preference, the proportion of voids will vary with the depth of the thin layer. Measured based on the total film thickness, 0 to 50% from the top layer of the thin layer is TiO₂, ZrO₂Or HfO₂It is preferably composed of. This material is thereby suitable for applications where the top layer requires electrical properties, such as insulators. The material of the present invention is preferably applied as a thin film coating to a metal substrate composed of molybdenum, silver, gold, copper, aluminum, tungsten, nickel, chromium, zirconium, titanium, hafnium, tantalum, niobium, vanadium, iron and alloys thereof. can do. The metal substrate can be applied to any other solid carrier. The metal substrate is preferably produced by a rolling or pouring method and contains impurities. The material of the invention formed as a thin film coating is preferably applied to a coarse substrate, the roughness of which is characterized by a statistical distribution that is a deviation from the average level, and the standard deviation of this distribution is 0. It is in the range of ~ 1,500 nm, preferably 40 ~ 120 nm. Roughness allows for better absorption at short wavelengths and therefore can be used as an absorber-reflector tandam. The material of the invention, formed as a thin layer, is one or more oxides, preferably SiO.₂, ZrO₂, HfO₂, Al₂O₃, Y₂O₃It can be covered with an additional thin layer consisting of. This layer, preferably thinner than 60 nm, allows the material to be passivated and extend its useful life. A layer system consisting of the material of the invention and preferably an oxide layer of 1-45 can be used as an antireflection filter. The depth of the layer system is therefore selected by the method of the algorithm, and as a result, the reflection over the specific wavelength range will be particularly high. Suitable algorithms can be obtained from the relevant literature (eg, Eisenhammer, T., M. Lazarov, N. Leitbacher, U. Schoffel and R. Sizmann. 1993. "Optimization of interference filters with genetic algorithms, applied to silver-base heat mirros". Applied Optics.32). Such coating systems to which the materials of the present invention are applied are capable of good absorption at specific wavelengths and have a reflection reducing effect. The total coating thickness of the antireflection layer product is increased by the index of refraction (measured in the visible wavelength region) of the oxide used, preferably in the range of 20-80 nm, preferably 80-110 nm. .. As mentioned earlier, the introduction of voids regulates the balance between various competing properties, such as electrical and metallic properties. In addition to the optical properties, the electrical properties can also be changed accordingly. Preferably, a resistivity of 3,500 μΩ · cm is provided by voids in the material at a rate of about 20-25% (% by volume). Only controlling the voids allows for controlled variations in resistivity and describes the effect of plasma wavelengths on optical properties. This alone makes it possible to control and design the properties of this material that are important for certain applications, eg, as selective absorbers. The materials of the invention having adjustable properties, which are electrical and temperature resistant, are useful in various sectors of the industry. In solar energy: If the material of the invention with voids of about 22-26% by volume is applied, preferably on copper, molybdenum or aluminum to a film thickness of preferably 40-70 nm, the selective absorbers can get. This absorber can convert incident solar radiation into heat at a temperature of about 400 ° C. without the need to concentrate the radiation. In addition, material properties are adapted by controlling the proportion of chemical compositions and voids for optimal yields from solar radiation as a function of desired temperature for thermal energy, climate and radiation concentration. For solar energy applications, the material is applied as a thin layer on a metal substrate (metal substrate), preferably of any shape and size (geometry), and the coating film thickness is preferably in the range of 40-80 nm. Selected, as a result, the combination of the thin layer and the metal substrate absorbs the wavelength as a selective absorber and converts the radiation coming from the sun into thermal energy. Preferably, the wavelength absorption is in the range of 0.3 to 1.5 μm. For application to solar energy, the material of the present invention is one in which the proportion of voids is preferably 20-30% by volume, the layer thickness is 40-70 nm, and the metal substrate used is preferably copper or aluminum. Is. In addition, the thickness is 70-120 nm, preferably 85-100 nm, and SiO₂An antireflection layer consisting of can be used. When used with solar energy, radiation energy is absorbed into the material, thereby warming the material and thermal energy is taken up by connecting to thermal carriers. The thermal carrier thereby becomes one or more phases of water. The absorber can be installed in any type of solar energy accumulator. -In the semiconductor industry: silver and gold are known to diffuse through a thin layer of TiN. Their diffusion rates are small and almost uncontrollable. According to the materials of the present invention, the diffusion rate can be greatly increased and the electrical properties of the layer can be set within a wide limit at the same time. In particular, the resistivity can be increased (preferably 1,000 to 30,000 μΩ · cm). Therefore, tempering makes it possible to produce circuit boards containing small amounts of silver and gold. As a paint for blades of lightweight mills: If a thin insulating slab, preferably made of mica or airgel, is coated with copper, silver or aluminum to a thickness of about 200-1,000 nm, and further the material of the invention is preferred. When applied to a thickness of 40-150 nm to produce a selective airgel, slabs with this converter are very suitable for use as blades of lightweight mills. -As a decorative layer: The material of the present invention is preferably suitable for use as a decorative layer, if the material is applied to a substrate to a thickness of 15-100 nm, preferably 30-50 nm. If so, the visual impression of color would be produced by the interference effect of this combination. The material and substrate are coated on it with a thin (about 60-120 nm), preferably partially transparent layer. In power generator technology: The material of the present invention is more suitable as a selective radiation emitter for converting thermal energy into electric power, which material is warmed and emits heat as a selective radiation transmitter, this Heat is converted into electric current by the photovoltaic cell. A substance having a void of 7 to 20% in volume and coated on a substrate (preferably molybdenum) having a thickness of 50 to 500 nm, preferably about 100 to 200 nm is preferable in the electric power industry as a selective emitter. used. Since the material of the present invention is temperature stable, this emitter can be heated to temperatures above 900 ° C. In medicine: The exchange between dielectric and metallic properties occurs on a scale in the nm range. For example, metals such as silver are known to have antimicrobial properties, where bacteria easily attach to the metal and form a film, where the bacteria die. New bacteria may also be present there, but they do not come into contact with the metal and are not killed. Dielectric substances have bacterial extermination properties. Since the substance of the present invention has both antimicrobial (metallic) and bacterial extermination (dielectric) properties, it kills bacteria but does not adhere and remain. The antimicrobial effect remains unchanged. This wide range of applications is obtained by controlling the physical properties with voids. This control can be simply predicted by Braggman's theory of effective medium, which considers the material to be a mixture of voids and layers present with the voids. It is a great advantage of the present invention that the desired optical and electrical properties cannot be adjusted solely by the chemical composition and are obtained by voids. Important properties such as adhesion, temperature stability, corrosion resistance, etc. can thereby remain unchanged, which are essentially determined by chemical properties. Further advantages of the present invention are Metals, nitrogen and oxygen of Group IVA of the Periodic Table, and the compounds produced from them are not toxic and are not toxic. Titanium, zirconium or hafnium and nitrogen and oxygen compounds are more stable, resistant (hardness) and lighter in temperature than metals such as iron or copper. That's what it means. Furthermore, an object of the present invention is achieved by the method of reactive vacuum deposition (or activation reactive vacuum deposition) according to claim 24. According to the present invention, the compound of oxide, nitride or carbide is at least N.₂, O₂, CH₄And / or by depositing a metal of Group IVA of the Periodic Table on the substrate while maintaining a gas atmosphere containing noble gases. Condensation of metal particles on a heatable substrate thereby results in a gas pressure P_tot, Vapor deposition rate r, substrate temperature T_subAnd the distance l between the metal source and the substrate, the volume ratio of the voids is 2 to 45% by volume, and their size is (0.5 nm).^３~ (100nm)^３It can be controlled by keeping it within the range of. The manufacturing parameters are selected as follows. T = 20-400 ° C, L = 0.01 to 1.5 m N₂Gas and O₂Gas partial pressure ratio: (P_N2/ P_O2) = 1 to 2,000, P_tot＝２×10^-5hPa ~ 4 × 10^-2hPa and R = 0.01 to 60 nanometers / s In the manufacturing parameters, it is necessary to set the manufacturing parameters so that the void capacity can be predicted. This can be achieved by the following method. The following equation holds for the substrate temperature in the range of preferably 100 to 220 ° C. and the distance l between the vapor deposition source in the range of preferably 0.5 to 1.2 m and the substrate. if,And the total gas pressure p_totIs 2x10^-3〜２×10^-2If in the hPa range, a void of 34% is achieved in percentage of volume. if,If it is in the range of, the void ratio of 20% is achieved. By selecting size K, a volume percentage between 20 and 34% is specified by the following formula. Therefore, in the material of the present invention, in order to achieve the desired void ratio, the total pressure p together with the ratio r._totWith, and with distance l, it is possible to achieve the desired proportion of voids in the material of the invention. Similarly, by the following method, the substrate temperature is preferably in the range of 250 to 400 ° C., and l is preferably in the range of 0.5 to 1.2 m, so that the volume percentage of the voids in the layer can be controlled. Become. if,And p_totIs 2x10^-2hPa ~ 4 × 10^-2If it is in the hPa range, a void of, for example, 40% is achieved in volume proportions. If K isIf the range of is selected, the volume percentage of the void is 20%. To achieve a value between 20 and 40%, K is the formula:Must be selected by. The percentage of capacity that exists between them can, of course, be determined by first-order interpolation. Small volume percentage voids (2-20%) have low velocities 0.01-0.1 nm / s and low gas pressure 10^-4Achieved by mBar. Very large void percentage (> 40%) has a high total gas pressure> 4 × 10^-2Obtained at mBar. At those gas pressures, the material can exist in a loosely bound state. In the present invention, the application of the substance is preferably applied to a substrate composed of molybdenum, silver, gold, copper, aluminum, tungsten, nickel, zirconium, hafnium, tantalum, niobium, vanadium, iron or alloys thereof. Two methods are suitable for producing a substance as a block without a substrate: -(PVD) deposition occurs at any thickness on NaCl, KBr or other salts. This salt then dissolves in water, after which the material of the invention remains. -Evaporation is carried out on thin metals with a low melting point, such as copper, aluminum, tin, zinc or bronze. The material and the substrate (base material) are then placed under high vacuum (10).^-10) And, of course, at a temperature near the melting point of the metal, resulting in evaporation of the metallic substrate. What remains behind is the substance of the present invention. The thickness of the coating film is arbitrary, preferably 30 to 120 nm. The gas atmosphere is preferably H₂It can contain volatile compounds of O and carbon. The manufacturing method can thereby be carried out cheaper. In many cases it is conceivable to completely replace oxygen with water or tolerate air. In the method of the present invention, the metal of Group VI A of the Periodic Table is vapor-deposited on a substrate placed in the apparatus at a distance of 0.01 to 1.5 m from the crucible in the vacuum-deposited chamber. The gas atmosphere is maintained by one or more gas meter valves or gas flow meters, and partial pressure measurements and adjustments are made by mass spectrometers. Gas atmosphere is gas type N₂, O₂, CH₄And at least one of the noble gases. The substrate temperature is adjusted by a regulator, preferably a PiD regulator, in the range of 20-400 ° C. The evaporation rate is measured with a quartz oscillator, and the signal controls the output of the evaporator by a regulator, preferably a PiD regulator. The desired evaporation is set. The above coating parameters are achieved by the above equipment. Further, the total gas pressure is determined by the total gas pressure meter. Used for evaporation are electron beam evaporators and / or resistance evaporators and / or induction evaporators. The apparatus of the present invention becomes inexpensive when a resistor or an induction evaporator is used. The substrate is preferably heated to a substrate temperature range of 20-400 ° C. required by a radiation heater. Induction heating or electronic resistance heating is also suitable. Evaporation of the metal is preferably carried out in a separable exhaust chamber, which is shuttered to the gas atmosphere and chamber containing the substrate. This change in practice allows high total pressure without reducing the operational life of the evaporator. The gas atmosphere mixture is preferably controlled by a separated gas flowmeter or mass spectrometer. p_totSuitable for measuring the magnitude of is, for example, a friction pressure gauge or a baratron. The gradient layer is also manufactured by the apparatus of the present invention. In those layers, the composition varies with coating depth. This is controlled by the composition of the gas to be introduced. N₂Increasing the amount gives a film containing more nitrogen. The composition of the gas can be adjusted by the influx or by measuring the partial pressure. If a friction pressure gauge is used, the apparatus of the present invention can provide reproducible coating properties. The substrate is the cos of the evaporator (n = 1 to 7)^II-A uniform coating is guaranteed over the entire surface if it is an elongated piece or foil formed by the property and conforms to the evaporator properties of the evaporator. Preferably, the coating chamber is connected to one or more additional coating chambers by a separate and evacuable vacuum tube, and the substrate passes from one chamber to the other without breaking the vacuum for another coating process. Attached. The result is a multi-layer system. The present invention will be described with reference to FIGS. 1-9. Figure 1 shows TiN_xO_y(×) and ZrN_xO_y（△）

Here, the imaginary part of the refractive index at 10 μm is shown as a function of the void percentage for x = 0.7 to 0.9; y = 0.3 to 0.6]. Figure 2 shows a 55 nm thick TiN as a function of void percentage._xO_y-Cu

[Here, x = 0.7 to 0.9; y = 0.3 to 0.6] The degree of sunlight absorption of the absorber is shown. Figure 3 shows a 55 nm thick TiN as a function of void percentage._xO_y

[Here, x = 0.7 to 0.9; y = 0.3 to 0.6] The degree of heat release of the absorber at 250 ° C. is shown. Figure 4 shows TiN_xO_y

Here, the elemental composition for titanium as a function of the partial pressure of oxygen in coating in the case of [x = 0.7 to 0.9; y = 0.3 to 0.6] is shown. Figure 5 shows TiN_xO_y(×) and ZrN_xO_y（△）

Here, the ratio of the coating mass density to the bulk density as a function of the ratio of voids in [x = 0.7 to 0.9; y = 0.3 to 0.6] is shown. Figure 6 shows TiN_xO_y

Here we show the real part of the index of refraction as a function of wavelength at various void percentages at [x = 0.7-0.9; y = 0.3-0.6]. Figure 7 shows TiN_xO_y

Here, the imaginary part of the refractive index as a function of the wavelength for various parts of the void in the case of [x = 0.7 to 0.9; y = 0.3 to 0.6] is shown. FIG. 8 shows a cross section of a selective solar absorber using the material of the present invention. FIG. 9 shows a cross section of an apparatus for producing the substance of the present invention. Example 1 In a high vacuum device, titanium and zirconium were evaporated by an electron beam evaporator in a mixed gas of nitrogen and oxygen. Nitrogen partial pressure is 2.5 to 9.5 x 10^-4It is mBar and the oxygen partial pressure is 1 × 10.^-8mBar ~ 8 × 10^-5I changed it in the range of mBar. Painting was performed on a copper disc with a thickness of 2 mm and a glass disc with a thickness of 1 mm. The substrate was kept at 170 ° C. during the process. The plasma discharge was ignited in the vessel by a surface electrode. This increases the ease of formation of TiN and TiO, or ZrN and ZrO in the layer. Prepared for analytical purposes are samples of various layer thicknesses (30-120 nanometers) and void percentages (5-32% by volume). N₂O₂The voltage division ratio to 35 was maintained at 35, and the distance of the substrate from the evaporator was 0.8 m. The void percentage was controlled by the evaporation rate and it was assumed to be the following values: 0.06 nm / s for low void percentages and up to 0.2 nm / s for high void percentages. The crystalline phases TiN and TiO, or ZrN and ZrO, were identified by an X-ray reflector. The elemental composition was measured by an elastic recording detector (ERD). The layer thickness and layer density were quantified by an X-ray reflector (GIXR) with a gaze incident line. The distribution of voids and their size was quantified by the measurement of scattered X-ray radiation by the gaze incident line. It is clear that the bulk density of the layer relative to the mass of TiO or TiN decreases with the percentage of void filling. For zirconium, there was a deviation of 3-5% from this rule. Sunlight absorption α_solDegree ofIs determined by measuring the degree of the desired hemispherical reflection ρ (λ). Here, AM15 (λ) is the standard sunlight spectrum AM1.5, and lambda is the wavelength of radiation. The degree of heat release was measured by a calorimetric method at a temperature of 150-400 ° C. The optical constants were determined by measuring reflectance and transmittance by a commonly known graphing method. The results are shown in FIGS. 1-7. They are described in detail here. Figure 1 shows TiN_xO_y(×) and ZrN_xO_yThe imaginary part of the refractive index at 10 μm as a function of the void part with respect to (Δ) is shown. Voids without voids are high and are typical metallic properties. The portion with 20% to 25% voids produces a mixed state of metallic and dielectric behavior. In both examples, it is clear that the portion with 20-30% voids can moderately reduce the index of refraction in the imaginary portion. This means that the degree of heat release can be kept low when applied as a solar absorber. The refractive index could be determined by an elliptical deflection measuring instrument or by measuring the degree of reflectance and transmittance. Percentages of voids and their size were determined by X-ray scatter or neutron scatter. Figure 2 shows a 55 nanometer thick TiN as a function of the percentage of voids._xO_y-Cu Indicates the degree of sunlight absorption of the absorber. By measuring the degree of reflectance of the absorber and the folding of the spectrum of solar radiation incident on the earth, the percentage of absorbed energy and the degree of solar absorption were determined. From a material with a percentage of voids of 27.5%, one with maximum absorption of incident sunlight radiation was obtained. Figure 3 shows TiN with a thickness of 55 nanometers as a function of percent void._xO_y-Indicates the degree of heat release of the Cu absorber at 250 ° C. The degree of heat release decreases as the proportion of voids increases, which can be explained by the decrease in metallic properties. To measure the degree of heat release, the sample must be placed at the measurement temperature, 250 ° C. in this example, under vacuum. It is achieved by a suitable structure that the sample loses only heat by radiation. The degree of emission is calculated from the energy balance. Figure 4 shows TiN_xO_yThe elemental composition for titanium as a function of the partial pressure of oxygen in the layer is shown. The ratio of nitrogen to oxygen was kept in the range of 1 to 2,000 for producing the substances of the invention in the apparatus of the invention. What is obtained by the low partial pressure of oxygen is a chemical property required for use as a selective absorber of solar energy, for example, high adhesiveness. Figure 5 shows TiN_xO_y(×) and ZrN_xO_yThe ratio of the layer mass density to the bulk density as a function of the void percentage in the case of (Δ) is shown. It is clear that the mass density is dominated by the percentage of voids. Figure 6 shows TiN_xO_yThe real part of the index of refraction as a function of wavelength at various void percentages in the case of a coating is shown. At the void ratio at 18% by volume, the real part of the index of refraction still exhibits metallic properties and rises with wavelength. At a rate of 22% by volume, neither metallic nor dielectric properties predominate, but at 32% by volume, the material is dielectric to the present invention. Figure 7 shows TiN_xO_yThe imaginary part of the index of refraction as a function of wavelength for various percent voids in the coating is shown. In the void portion at 18% by volume, the imaginary part of the refractive index still exhibits metallic properties and rises with wavelength. At a rate of 22% by volume, neither metallic nor dielectric properties predominate, but at 32% by volume, the material is dielectric over a wide wavelength range. FIG. 8: An application example of the substance of the present invention is shown in FIG. What is shown in FIG. 8 is a cross section of a selective solar absorber, in which the substance (2) of the present invention is used. A 55-nanometer-thick coating of the material (2) of the present invention is applied onto the copper of the highly reflective substrate (1), and the latter is a 92-nanometer-thick SiO.₂It is covered with an antireflection layer made of (3). This anti-reflection layer increases the degree of sunlight absorption from 0.8 to 0.94. The substance (2) of the present invention is characterized by a void content of 27.5% by volume and a titanium: oxygen: nitrogen ratio of 1: 0.92: 0.35. FIG. 9 shows a cross section of the manufacturing apparatus of the present invention. The copper piece (2) covers the electron beam evaporator (1). The curved surface shape is maintained by the roller (3) so that the coating is uniform. The curved surface follows the characteristics of the evaporator and is different from that of the Lambert radiator. The characteristics of the Lambert radiator are "cosine".^１Although it can be described by "the law of", the modification of the law must also be considered in the case of electron beam evaporators, that is, "cosine".ⁿThe characteristic of "is in the range of 1 to 7 of n.

Continuation of front page (56) References Japanese Patent Application Laid-Open No. 4-195125 (JP, A) Japanese Patent Application Laid-Open No. 4-228426 (JP, A) Japanese Patent Application Laid-Open No. 64-37408 (JP, A) Japanese Patent Application Laid-Open No. 60-65069 (JP, A) Japanese Patent Application Laid-Open No. 1-215718 (JP, A) Japanese Patent Application Laid-Open No. 1-1141963 (JP, A) JP-A-5-254887 (JP, A) Japanese Patent Application Laid-Open No. 1-216242 (JP, A) Japanese Patent Application Laid-Open No. 5-239636 (JP, A) Japanese Patent Application Laid-Open No. 4-329864 (JP, A) (58) Surveyed field (Int.Cl.⁷, DB name) C23C 14/00 --14/58 C01B 21/082 C01G 23/00 C01G 25/00