WO2022202640A1 - 透明導電膜、透明導電膜の製造方法、透明導電部材、電子ディスプレイ機器、および太陽電池 - Google Patents

透明導電膜、透明導電膜の製造方法、透明導電部材、電子ディスプレイ機器、および太陽電池 Download PDF

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WO2022202640A1
WO2022202640A1 PCT/JP2022/012476 JP2022012476W WO2022202640A1 WO 2022202640 A1 WO2022202640 A1 WO 2022202640A1 JP 2022012476 W JP2022012476 W JP 2022012476W WO 2022202640 A1 WO2022202640 A1 WO 2022202640A1
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Prior art keywords
transparent conductive
conductive film
film
alkali
tungsten bronze
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PCT/JP2022/012476
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English (en)
French (fr)
Japanese (ja)
Inventor
健治 足立
啓一 佐藤
秀晴 大上
里司 吉尾
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to CN202280022878.8A priority Critical patent/CN117062937A/zh
Priority to KR1020237031071A priority patent/KR20230158488A/ko
Priority to JP2023509114A priority patent/JPWO2022202640A1/ja
Priority to US18/551,276 priority patent/US20240177883A1/en
Priority to EP22775428.0A priority patent/EP4317522A4/en
Publication of WO2022202640A1 publication Critical patent/WO2022202640A1/ja
Anticipated expiration legal-status Critical
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Definitions

  • the present invention relates to a transparent conductive film, a method for manufacturing a transparent conductive film, a transparent conductive member, an electronic display device, and a solar cell.
  • Transparent conductive films are used for liquid crystal display elements, transparent electrodes for solar cells, infrared absorbing and reflecting films, and electromagnetic wave shielding films.
  • liquid crystal display elements are actively being used in OA equipment such as personal computers and word processors, and the demand for transparent electrodes is increasing accordingly.
  • the material contains a large number of conduction electrons (free electrons), has high conductivity, and is relatively easy to pattern by etching.
  • Doped ITO Indium-Tin-Oxide
  • Patent Documents 1 and 2 and Non-Patent Document 1 is mainly used (see Patent Documents 1 and 2 and Non-Patent Document 1).
  • In 2 O 3 which is the base of ITO, is an oxide semiconductor, and is a transparent conductive material that exhibits electrical conductivity by supplying carrier electrons by introducing oxygen defects into the crystal. It is believed that when Sn is added to In 2 O 3 , the trivalent In sites are replaced with tetravalent Sn, thereby further increasing carrier electrons and exhibiting high conductivity.
  • the ITO conductive film has excellent visible light transmittance and film surface resistance, but it is expensive because it uses indium. For this reason, the physical properties of transparent conductive films have been improved and the cost has been reduced by improving ITO film formation technology and sputtering targets. It's getting difficult.
  • AZO, GZO zinc oxide
  • carrier electrons are supplied by substituting divalent Zn sites with trivalent Al or Ga, resulting in highly conductive transparent conductive materials.
  • AZO and GZO have been considered to be first candidate materials for ITO replacement because they can provide transparent conductivity close to that of ITO.
  • AZO and GZO have drawbacks in that the conditions for exhibiting conductivity are narrow, and their heat resistance and weather resistance are considerably inferior to those of ITO (Non-Patent Document 1).
  • Tin oxide has long been known as a transparent conductive material to replace ITO. Tin oxide is superior to ITO in chemical and thermal stability and visible light transmittance (visible light transparency), and is therefore used for electrodes for solar cells. However, tin oxide, even if its specific resistance is reduced by antimony doping or partial fluorine substitution of oxygen, has considerably lower conductivity than ITO and is inferior in etching properties. For this reason, tin oxide is not used as electrodes for displays (Non-Patent Document 1).
  • the present applicant has proposed a tungsten oxide represented by the general formula WyOz ( 2.2 ⁇ z / y ⁇ 2.999 ), and the general formula M
  • a transparent conductive film of a composite tungsten oxide represented by x W y O z was proposed (see Patent Document 3).
  • the M element of the composite tungsten oxide is one or more elements selected from H, He, alkali metals, alkaline earth metals, rare earth elements, other transition metals, etc., and 0.001 ⁇ x/y ⁇ 1, 2.2 ⁇ z/y ⁇ 3.0.
  • Patent Document 3 a solution containing a raw material compound of tungsten oxide or/and composite tungsten oxide or/and composite oxide is applied to a substrate and then heat-treated in a reducing gas or/and inert gas atmosphere. , also discloses a method for producing a transparent conductive film for producing the transparent conductive film.
  • Patent Document 4 discloses a technique for an infrared shielding film using a composite tungsten oxide film formed by a sputtering method.
  • Non-Patent Document 2 Cs 0.32 WO 3 having a hexagonal tungsten bronze structure has been reported to have a single crystal room temperature resistivity of 5.5 ⁇ 10 ⁇ 5 ⁇ cm. However, this potential high conductivity has not been realized as a dry thin film.
  • transparent conductive films of tungsten oxide and composite tungsten oxide have been proposed as one of the candidates for the transparent conductive film to replace ITO.
  • no transparent conductive film having a high electrical conductivity with a specific resistance of less than 5.2 ⁇ 10 ⁇ 2 ⁇ cm has been found in general dry continuous film production methods such as the sputtering method.
  • one aspect of the present invention aims to provide a transparent conductive film with excellent conductivity.
  • a transparent conductive film comprising alkali tungsten bronze, wherein the alkali tungsten bronze exhibits a hexagonal crystal pattern in a powder X-ray diffraction pattern, and is free of orthorhombic, trigonal, and pyrochlore phase shifts.
  • One aspect of the present invention can provide a transparent conductive film with excellent conductivity.
  • FIG. 1 is a powder X-ray diffraction pattern of the transparent conductive film obtained in Example 1.
  • FIG. 2 is a powder X-ray diffraction pattern of the film obtained in Comparative Example 3.
  • FIG. 1 is a powder X-ray diffraction pattern of the transparent conductive film obtained in Example 1.
  • FIG. 2 is a powder X-ray diffraction pattern of the film obtained in Comparative Example 3.
  • this embodiment Specific examples of a transparent conductive film, a method for manufacturing a transparent conductive film, a transparent conductive member, an electronic display device, and a solar cell according to an embodiment of the present disclosure (hereinafter referred to as "this embodiment") are shown below with reference to the drawings. I will explain as I go along. The present invention is not limited to these exemplifications, but is indicated by the scope of the claims, and is intended to include all modifications within the scope and meaning equivalent to the scope of the claims.
  • a bar (-) is added above the number for a negative index, but a minus sign (-) is added before the number in the following description.
  • a "" is added between the exponent numbers.
  • the suffix H means a hexagonal crystal, O an orthorhombic crystal, R a trigonal crystal, and P a pyrochlore phase. Two surfaces whose reflections overlap at the same diffraction angle are shown with a "/" between the Miller indices representing each surface.
  • Transparent conductive film The inventors of the present invention used the skeleton structure of tungsten trioxide, which is a wide bandgap material that transmits light in the visible light region, as a material for the transparent conductive film, and reduced the amount of oxygen and added cations to We focused on tungsten bronze, which is a material that generated conduction electrons.
  • tungsten bronze which is a material that generated conduction electrons.
  • alkali tungsten bronzes alkali composite tungsten oxides having a hexagonal crystal structure as composite tungsten oxides have high visible light transmittance and are the most promising as transparent conductive films. predicted that.
  • the orthorhombic crystal is a structure in which stacking faults occur in the hexagonal prism planes, and the structure in which the defects are regularly inserted is the orthorhombic Cs 4 W 11 O 35 .
  • the trigonal and cubic pyrochlore phases are those in which stacking faults occur on the basal plane of the hexagonal crystal, and the structures in which defects are regularly inserted are trigonal Cs 6 W 11 O 36 and trigonal Cs 8.5 W 15 .
  • O 48 pyrochlore phase (Cs 2 O) 0.44 W 2 O 6 .
  • the orthorhombic Cs 4 W 11 O 35 is associated with planar defects on the prism surface, and the trigonal Cs 6 W 11 O 36 , Cs 8.5 W 15 O 48 , and pyrochlore phase are associated with planar defects on the bottom surface. ( Cs2O ) 0.44W2O6 appears .
  • FIG. 1 The top row of FIG. 1 is the powder X-ray diffraction pattern of the hexagonal tungsten bronze film obtained in Example 1, which will be described later.
  • FIG. 1 shows the data of the powder X-ray diffraction pattern database.
  • (A) is the profile of hexagonal Cs 0.32 WO 3
  • (B) is the orthorhombic Cs 4 W 11 O 35 profile
  • (C) is the trigonal Cs 6 W 11 O 36 profile.
  • FIG. 2 is the powder X-ray diffraction pattern of the pyrochlore phase-shifted (pyrochlore-shifted) film obtained in Comparative Example 3 described later.
  • (A) is the profile of hexagonal Cs 0.32 WO 3 and
  • (B) is the profile of pyrochlore phase (Cs 2 O) 0.44 W 2 O 6 .
  • the (0,16,0) O and (480) O are (10-12) H and (20-20) H peaks, respectively. Increase width.
  • weak peaks such as (252) O , (082) O , and (232) O appear on the low angle side of (20-20) H.
  • the intensity distribution and the positions of these extra diffraction lines may deviate from the positions and intensities of the diffraction lines of the orthorhombic, trigonal, and pyrochlore phases.
  • the orthorhombic, trigonal, and pyrochlore phases which appear to be mixed in the hexagonal crystal, are not simply a mixture of separated crystal phases, but the insertion plane and amount of stacking faults change in one hexagonal crystal. This suggests that the powder X-ray diffraction pattern has changed.
  • Non-Patent Document 3 Hydrogen derived from water bonds with oxygen in the crystal, but because it competes with alkali metal element ions such as Cs + and W 6+ in the crystal, W defects and W defects occur on the base of the hexagonal crystal and the prism surface depending on the charge neutrality condition.
  • the plane spacing expands slightly due to local ion repulsion on the plane where the W defect or the Cs defect occurs. Due to this expansion, the crystal loses its hexagonal symmetry and becomes orthorhombic, trigonal, and cubic.
  • the transparent conductive film of the present embodiment contains alkali tungsten bronze, and the alkali tungsten bronze exhibits a hexagonal crystal pattern in a powder X-ray diffraction pattern, and is free of orthorhombic, trigonal, and pyrochlore phase shifts.
  • the alkali tungsten bronze possessed by the transparent conductive film of the present embodiment exhibits a hexagonal pattern in a powder X-ray diffraction pattern and has a structure free from orthorhombic, trigonal, and pyrochlore phase shifts. will form the original hexagonal tungsten bronze structure. As a result, free electrons are generated, and a transparent conductive film having excellent conductivity can be obtained.
  • the transparent conductive film of the present embodiment can also be made of the alkali tungsten bronze. However, even in this case, it is not excluded that the transparent conductive film of the present embodiment contains unavoidable impurities during the manufacturing process.
  • the powder X-ray diffraction pattern of alkali tungsten bronze is on the low angle side and the high angle side of the diffraction peaks of hexagonal crystals (10-12) H and (20-20) H , It is preferable not to have extra peaks derived from orthorhombic, trigonal, and pyrochlore phases.
  • the transparent conductive film of the present embodiment can also contain a small amount of heterogeneous phase as long as it can be a transparent conductive film having excellent conductivity.
  • the criteria for judging surplus peaks are not particularly limited. For example, when the intensity of the (20-20) H peak, which is the maximum intensity peak of hexagonal alkali tungsten bronze, is set to 1, the maximum intensity peak derived from the orthorhombic, trigonal, and pyrochlore phases is 0.5. In the case of 25 or less, it can be determined that there is no surplus peak.
  • the alkali tungsten bronze contained in the transparent conductive film of the present embodiment has the general formula A x W y O z (0.2 ⁇ x/y ⁇ 0.5, 2.5 ⁇ z/y ⁇ 3.0, element A is preferably represented by one or more alkali metal elements selected from K, Rb, and Cs).
  • the alkali tungsten bronze contained in the transparent conductive film of the present embodiment has the general formula A x W y O z (0.2 ⁇ x/y ⁇ 0.5, 2.5 ⁇ z/y ⁇ 3.0)
  • element A is one or more alkali metal elements selected from K, Rb, and Cs
  • part of element A is represented by Na, Tl, In, Li, Be, Mg, Ca, Sr, Ba, Al , and Ga.
  • the alkali tungsten bronze contained in the transparent conductive film of the present embodiment has the general formula A x-a M a W y It can also be written as Oz .
  • M in the above general formula is the substitution element M, and a corresponds to the substitution amount of the element A with the substitution element M, satisfying 0 ⁇ a ⁇ x. Since the elements A, x, y, and z have already been described, the description thereof is omitted.
  • the degree and ratio of substituting the element A with the above-mentioned substituting element are not particularly limited, and can be arbitrarily selected according to the required properties and the like.
  • the lattice constant of the alkali tungsten bronze contained in the transparent conductive film of this embodiment is not particularly limited.
  • the lattice constant of the hexagonal c-axis is 7.54 ⁇ or less when the element A is K, 7.58 ⁇ or less when the element A is Rb, and 7.58 ⁇ or less when the element A is Cs. It is preferably 64 ⁇ or less.
  • the lattice constant of the hexagonal c-axis is 7.49 ⁇ or more and 7.54 ⁇ or less when the element A is K, and 7.51 ⁇ or more and 7.58 ⁇ or less when the element A is Rb. is Cs, it is more preferably 7.56 ⁇ or more and 7.64 ⁇ or less.
  • the alkali tungsten bronze is more reliably hexagonal, which means that there is no orthorhombic, trigonal, or pyrochlore phase shift as described above.
  • the film thickness of the transparent conductive film of the present embodiment is not particularly limited, it is preferably 30 nm or more and 1200 nm or less.
  • the transparent conductive film of the present embodiment is a film obtained by sputtering film formation or the like, so that it can be formed thinly and uniformly without using a dispersant or a medium resin.
  • the transparent conductive film of the present embodiment By setting the film thickness of the transparent conductive film of the present embodiment to 30 nm or more, the transparent conductive film can have a particularly low resistance value.
  • the film thickness of the transparent conductive film of the present embodiment is 1200 nm or less, coloration of the film can be suppressed.
  • the amount of target used during manufacturing can be reduced, the time required for sputtering film formation can be reduced, and productivity can be improved.
  • the specific resistance value of the transparent conductive film of this embodiment is preferably, for example, 1.0 ⁇ 10 ⁇ 2 ⁇ cm or less, more preferably 5.0 ⁇ 10 ⁇ 3 ⁇ cm or less.
  • the transparent conductive film of the present embodiment preferably has a visible light transmittance of 50% or more.
  • Method for producing transparent conductive film Next, one structural example of the method for manufacturing the transparent conductive film of this embodiment will be described. According to the method for manufacturing a transparent conductive film of the present embodiment, the above-described transparent conductive film can be manufactured. For this reason, the description of some of the matters that have already been described will be omitted.
  • the method for manufacturing the transparent conductive film of the present embodiment can have the following film forming process and heat treatment process.
  • an untreated film containing elements that constitute alkali tungsten bronze can be formed on the surface of the base material.
  • the untreated film can be heat treated.
  • the film formation process is preferably performed under film formation conditions that do not allow moisture to enter the non-heat-treated film.
  • an untreated film can be formed by, for example, a dry method.
  • raw materials used for forming an unheated film in the film formation step for example, a tungsten source and an alkali metal element source, which can constitute alkali tungsten bronze, can be used.
  • a composite tungsten oxide having a specific composition can also be used as the raw material.
  • tungsten source one or more selected from tungsten and tungsten compounds can be used.
  • alkali metal element source one or more selected from compounds of alkali metal elements and hydrates of compounds of alkali metal elements can be used.
  • tungstic acid H 2 WO 4
  • Tungsten trioxide powder obtained by baking tungstic acid may be used as a raw material for the tungsten source, or a commercially available tungsten trioxide powder may be used.
  • Tungsten oxide and composite tungsten oxide can also be used as the tungsten source.
  • a tungsten oxide powder represented by W y O z (where W is tungsten, O is oxygen, and 2.2 ⁇ z/y ⁇ 3.0) may be used.
  • the composite tungsten oxide for example, the general formula A x W y O z (where A is the element A, W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, 2.2 ⁇
  • a composite tungsten oxide powder represented by z/y ⁇ 3.0 can also be used.
  • the raw material used for forming the unheated film it is preferable to use, for example, a raw material obtained by mixing a tungsten source and an alkali metal element source so that the unheated film formed has a target composition.
  • raw materials for example, mixed powder obtained by mixing tungstic acid (H 2 WO 4 ) and one or more selected from oxides and hydroxides of alkali metal elements, tungsten trioxide, and oxidation of alkali metal elements. It is possible to use a mixed powder in which one or more kinds selected from substances and hydroxides are mixed.
  • a mixed powder obtained by mixing a mixture of tungstic acid (H 2 WO 4 ) and tungsten trioxide particles with one or more selected from oxides and hydroxides of alkali metal elements, tungstic acid (H 2 WO 4 ) and tungsten trioxide powder, and one or more selected from an aqueous solution of a metal salt of an alkali metal element, a colloidal solution of a metal oxide, and an alkoxy solution, and dried. It is also possible to use a product powder obtained by firing the dried powder in an inert gas atmosphere or a mixed gas atmosphere of an inert gas and a reducing gas.
  • tungstic acid H 2 WO 4
  • tungsten trioxide powder one or more selected from aqueous solutions of metal salts containing alkali metal elements, colloidal solutions of metal oxides, and alkoxy solutions.
  • the partner ions for forming the salt are not particularly limited, and examples thereof include nitrate ions, sulfate ions, chloride ions, and carbonate ions.
  • the drying temperature and time are not particularly limited.
  • the element A is selected from K, Rb, and Cs as described above.
  • One or more alkali metal elements can be used.
  • element A may be partially substituted with one or more elements selected from Na, Tl, In, Li, Be, Mg, Ca, Sr, Ba, Al, and Ga.
  • the non-heat-treated film can be formed, for example, using a pellet or a sintered target obtained by molding the above raw material.
  • the film formation method for the non-heat-treated film is preferably vacuum vapor deposition film formation or sputtering film formation.
  • a method for forming the non-heat-treated film it is more preferable to use a sputtering method using a sputtering target.
  • a DC sputtering deposition method in which a DC voltage is applied to a target is more preferable. This is because the power supply configuration is simple and the productivity is excellent.
  • the sputtering target may contain an alkali metal element constituting alkali tungsten bronze and tungsten.
  • the sputtering target is preferably either a sputtering target composed of alkali tungsten bronze or a sputtering target composed of a precursor containing an alkali metal element and tungsten.
  • a sputtering target using the raw material described above.
  • the composition is not particularly limited.
  • the A/W ratio which is the composition ratio of the amount of the element A (A) and the tungsten element (W) contained in the sputtering target, is preferably 0.2 or more and 0.7 or less, and 0.2 or more and 0.2 or more. 0.5 or less is more preferable. This is because it is reflected in A/W, which is the substance amount ratio between the element A and the tungsten element contained in the untreated film to be obtained.
  • the polygonal state target described in Patent Document 4 mentioned above may be used.
  • the crystal structure of the target is not particularly limited because it does not directly affect the crystal structure of the film.
  • the sputtering target preferably has a relative density of 70% or more and a specific resistance of 1 ⁇ cm or less.
  • a sputtering target can be produced, for example, by hot-press sintering a composite tungsten oxide powder in vacuum or in an inert atmosphere. This is because the sintered body produced in this manner has strength to withstand the machining in target production and the brazing temperature during bonding, and has electrical conductivity capable of direct-current sputtering.
  • the method for forming the unheat-treated film is not limited to the use of the sintered body target of the composite tungsten oxide.
  • an untreated film may be formed by a binary sputtering method using a target of A x O z , which is an oxide of an alkali metal element, and a target of W y O z , which is a tungsten oxide.
  • the sputtering power is applied such that the A/W ratio, which is the compositional ratio of the amount of the element A (A) and the tungsten element (W) in the untreated film to be obtained, is 0.2 or more and 0.7 or less.
  • the A/W ratio is preferably 0.2 or more and 0.5 or less.
  • the base material (substrate) on which the untreated film is formed is not particularly limited, but glass is preferred. This is because glass is transparent in the visible light region and is less likely to deteriorate or deform in the subsequent heat treatment process.
  • the thickness of the glass is preferably 0.1 mm or more and 10 mm or less. However, the thickness is not particularly limited as long as the thickness is commonly used for architectural window glass, automotive glass, display devices, and the like.
  • a load-lock type sputtering apparatus in order to minimize the contamination of the sputtered film, which is an untreated film, with moisture.
  • a turbo-molecular pump can be used for exhausting the sputtering apparatus, but in order to exhaust the moisture more efficiently, it is more preferable to add means for condensing and exhausting the moisture, such as a cryo-coil or a cryopanel.
  • the film formation conditions are such that moisture does not enter the untreated film when forming the untreated film.
  • the water pressure in the chamber is less than 1 ⁇ 10 ⁇ 4 Pa when the untreated film is formed.
  • the water pressure here means the water pressure in the atmosphere immediately before introducing the sputtering gas for forming the untreated film after the chamber is evacuated.
  • the ultimate vacuum in the chamber for forming the non-heat-treated film is less than 1 ⁇ 10 ⁇ 4 Pa.
  • the ultimate vacuum here means the ultimate vacuum just before introducing a sputtering gas for forming an untreated film after exhausting the inside of the chamber.
  • the chamber In order to achieve the above water pressure and ultimate vacuum, it is preferable to evacuate the chamber using the turbomolecular pump or the like while heating the inside of the chamber after placing the target or base material in the chamber.
  • a gas such as nitrogen gas
  • the sputtering gas can be supplied into the chamber.
  • the chamber may be evacuated again after dummy sputtering is performed with the shutter between the substrate and the target closed. In this case, it is preferable that the water pressure and the ultimate vacuum are satisfied even in the evacuation after the dummy sputtering. Then, after the chamber is evacuated, it is preferable to supply a sputtering gas into the chamber and perform film formation.
  • the moisture removal step includes, for example, a preheating degassing step of purging the moisture in the chamber with an inert gas or the like, and a first exhausting step of evacuating the inside of the chamber after setting the target or base material in the chamber. and a first sputtering gas supply step of supplying the sputtering gas into the chamber.
  • a dummy sputtering step in which dummy sputtering is performed as necessary, and after the dummy sputtering step, a second evacuation step in which the inside of the chamber is evacuated again can be performed.
  • the second exhausting step it is preferable to perform the second sputtering gas supply step of supplying the sputtering gas into the chamber, and then perform the film forming step of forming an unheated film on the substrate surface.
  • the degree of ultimate vacuum reaches less than 1 ⁇ 10 ⁇ 4 Pa in both the first evacuation step and the second evacuation step.
  • the sputtering gas used for forming the untreated film is not particularly limited, it is preferable to use, for example, argon gas or a mixed gas of argon gas and oxygen. Although nitrogen gas can be used instead of argon gas, argon gas can be used more preferably.
  • argon gas or a mixed gas of argon gas and oxygen gas when forming an untreated film is related to the next heat treatment step.
  • the oxygen concentration in the mixed gas is preferably less than 20% by volume, more preferably 3% by volume or more and 10% by volume or less.
  • the optimum oxygen concentration can be selected depending on the film formation conditions, since it greatly depends on the time taken for oxygen to be incorporated into the untreated film, which is a sputtered film, that is, the film formation rate.
  • the sputtering gas used in the film forming process that is, supplied in the second sputtering gas supply process, for example, preferably has a high purity.
  • the sputtering gas purity is preferably 3N or higher, more preferably 4N or higher, and further preferably 5N or higher. This is because, by increasing the purity of the sputtering gas, it is possible to suppress the moisture pressure in the chamber during the film formation process, thereby suppressing impurities such as moisture from entering the untreated film.
  • the sputtering gas in the dummy sputtering process that is, the sputtering gas supplied in the first sputtering gas supplying process, preferably has a high purity, and the sputtering gas purity is preferably 3N or higher. 4N or more is more preferable, and 5N or more is even more preferable.
  • the argon gas purity is preferably 99.9% or more, the oxygen concentration is less than 0.1%, and the hydrogen concentration is less than 1 ppm. More preferably, the argon gas purity is 99.999% or more, the oxygen concentration is less than 0.2 ppm, and the hydrogen concentration is less than 0.5 ppm.
  • a film formed by sputtering at room temperature without heating the substrate is usually amorphous, but diffraction peaks based on crystals may appear in X-ray diffraction analysis. This is because a hexagonal crystal structure is formed again in the subsequent heat treatment step.
  • the untreated film obtained in the film forming step can be heat treated to form a hexagonal crystal structure.
  • the unheated film is formed at 400° C. or more and less than 1000° C. in an atmosphere selected according to the oxygen content of the unheated film, specifically in an inert atmosphere, a reducing atmosphere, or an oxidizing atmosphere. Can be heat treated.
  • the purpose of heat treatment can be, for example, the formation of hexagonal crystals and the reduction of octahedral oxygen. Therefore, in the heat treatment step, the untreated film may be heat treated at, for example, 400° C. or more and less than 1000° C. in an inert atmosphere or a reducing atmosphere.
  • Alkali tungsten bronze having a hexagonal crystal structure with high crystallinity can be formed by heat-treating the unheat-treated film obtained in the film formation process.
  • the atmosphere it is preferable to select the atmosphere according to the gas during the sputtering film formation so that the oxygen concentration of the resulting film is within an appropriate range.
  • Either the film formation process or the heat treatment process may be performed in an atmosphere containing oxygen.
  • the heat treatment of the untreated film in the heat treatment step is performed at 400° C. or more and less than 1000° C. in an inert gas atmosphere or a reducing atmosphere.
  • the heat treatment is preferably performed at a temperature of from 400°C to 950°C.
  • nitrogen gas, argon gas, mixed gas of hydrogen and nitrogen, mixed gas of hydrogen and argon, or the like can be used.
  • the heat treatment temperature is preferably 400°C or higher and lower than 1000°C as described above.
  • the heat treatment temperature is preferably 400°C or higher and lower than 1000°C as described above.
  • the heat treatment temperature to less than 1000°C, the reaction between the transparent conductive film and the substrate can be suppressed, and deformation of the substrate and peeling of the transparent conductive film can be suppressed.
  • the heat treatment time is not particularly limited, but can be, for example, 10 minutes or more and 60 minutes or less.
  • the oxygen concentration of the untreated film is considered to be moderate or too low.
  • conductivity can be obtained even if the heat treatment is performed with an inert gas such as nitrogen gas that does not contain oxygen.
  • Conductivity can be obtained in a wide temperature range by heat-treating with an inert gas such as nitrogen gas that does not contain oxygen.
  • the heat treatment may be performed in an oxidizing atmosphere containing oxygen. Heat treatment in an oxidizing atmosphere containing oxygen can maintain the oxygen concentration in the film in a more appropriate range, and can further increase the conductivity.
  • the heat treatment is preferably performed in the heat treatment atmosphere of air or in an atmosphere with an oxygen concentration of 5% by volume or more and 20% by volume or less.
  • the heat treatment furnace when the heat treatment atmosphere is an air atmosphere does not have to have a special closed structure.
  • the heat treatment temperature is preferably 400° C. or higher and lower than 1000° C., and more preferably 400° C. or higher and 950° C. or lower.
  • the alkali tungsten bronze contained in the transparent conductive film can be sufficiently crystallized and various defects can be suppressed. Therefore, it is possible to form a transparent conductive film having an appropriate electronic structure and particularly excellent conductivity.
  • the heat treatment temperature to less than 1000° C.
  • excessive progress of oxidation can be suppressed, and a transparent conductive film having particularly excellent conductivity can be obtained.
  • the reaction between the transparent conductive film and the substrate can be suppressed, and deformation of the substrate and peeling of the transparent conductive film can be suppressed.
  • the heat treatment time is not particularly limited, but can be, for example, 10 minutes or more and 60 minutes or less.
  • the transparent conductive member of this embodiment can have a substrate and the above-described transparent conductive film disposed on the surface of the substrate.
  • the above-mentioned transparent conductive film has excellent conductivity, it can be used for various purposes such as transparent electrodes for displays and transparent electrodes for solar cells.
  • an electronic display device including the transparent conductive member of the present embodiment and a solar cell including the transparent conductive member of the present embodiment can be used.
  • the lattice constant of the crystal phase was determined by the Pawley method assuming a space group of P6 3 /mcm using calculation software DIFFRAC TOPAS from BRUKER AXS. (1-4) Visible Light Transmittance, Solar Transmittance, and Near-Infrared Reflectance ° Incident diffuse reflectance was measured.
  • the visible light transmittance (VLT) and the solar transmittance (ST25) of 300 nm or more and 2500 nm or less were determined according to JIS R 3106 (2019). Also, the near-infrared reflectance ( ⁇ ) at 780 nm or more and 2500 nm or less was calculated according to JIS K 5602 (2008).
  • (1-5) Composition The composition of alkali tungsten bronze in the obtained film was determined by chemical analysis. Alkali metal elements and tungsten were analyzed by an ICP emission spectrometer (manufactured by Shimadzu Corporation, model: ICPE-9000).
  • Cs cesium
  • W tungsten
  • CsWO powder dark blue composite tungsten oxide powder
  • This CsWO powder was put into a hot press and sintered under the conditions of a vacuum atmosphere, a temperature of 950° C. and a pressing pressure of 250 kgf/cm 2 to produce a CsWO sintered body.
  • Cs/W which is the ratio of the amounts of Cs and W
  • This oxide sintered body was machined to have a diameter of 153 mm and a thickness of 5 mm, and was bonded to a stainless steel backing plate using metallic indium brazing material to prepare a CsWO target.
  • a sputtering device manufactured by ULVAC, model number SBH2306) was used in the film formation process.
  • the opening and closing of the chamber of this sputtering apparatus is of a load-lock type, and the exhaust in the chamber is by a turbomolecular pump.
  • warm water of 60°C is introduced into the water-cooling pipes that are stretched around the entire outer wall of the chamber to heat it. Nitrogen gas was introduced, and the chamber was exposed to the atmosphere while evacuating moisture (preheating degassing).
  • the aforementioned CsWO target and Ti target were mounted on the sputtering apparatus.
  • a glass substrate (EXG manufactured by Corning, thickness 0.7 mm) was attached to the sputtering apparatus.
  • the chamber is evacuated to an ultimate vacuum of 10 -3 Pa by a dry pump, turbomolecules and a cryo-coil (moisture condensation), and then the sheath heater and substrate heater inside the chamber are turned off. While maintaining the temperature at 300° C., the gas was evacuated to the level of 10 ⁇ 5 Pa.
  • the chamber was evacuated until the water pressure in the chamber reached 2.0 ⁇ 10 ⁇ 5 Pa.
  • Table 1 shows the degree of ultimate vacuum at this time.
  • the shutter between the glass substrate and the target was opened, and the CsWO film was formed under the conditions of a sputtering gas pressure of 0.6 Pa and an input power of DC 600 W. was deposited to a thickness of 40 nm.
  • a quadrupole mass spectrometer was used to measure the water pressure.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the film thickness of the obtained transparent conductive film was 39.6 nm.
  • a specific resistance value of 2.5 ⁇ 10 ⁇ 4 ⁇ cm was obtained, confirming high conductivity.
  • the main visible light part with a wavelength of 400 nm or more and 780 nm or less was largely transmitted, while a large near-infrared reflection was observed in the near-infrared part with a wavelength of over 800 nm.
  • a near infrared reflectance of 61.2% was obtained for a visible light transmittance of 68.1%. Therefore, while maintaining sufficient transparency of VLT ⁇ 50% in the visible light region, it has metallic conductivity with a specific resistance value ⁇ of 1.0 ⁇ 10 -2 ⁇ cm or less and emits light in the near infrared region. It was confirmed that the film was a transparent conductive film that reflected and had high heat ray shielding performance.
  • Table 1 shows the conditions for producing the transparent conductive film
  • Table 2 shows the evaluation results of the obtained transparent conductive film.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the obtained transparent conductive film had transparency with a visible light transmittance of 67.5%, metallic conductivity with a specific resistance value of 5.4 ⁇ 10 ⁇ 4 ⁇ cm, and near-infrared reflection. It was found to be a transparent conductive film having a heat ray reflection performance of 48.4%.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the obtained transparent conductive film had transparency with a visible light transmittance of 63.8%, metallic conductivity with a specific resistance value of 9.6 ⁇ 10 ⁇ 4 ⁇ cm, and near-infrared reflection. It was found to be a transparent conductive film having a heat ray reflection performance of 58.8%.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the obtained transparent conductive film had transparency with a visible light transmittance of 65.4%, metallic conductivity with a specific resistance of 6.9 ⁇ 10 ⁇ 4 ⁇ cm, and near-infrared reflection. It was found to be a transparent conductive film having a heat ray reflection performance of 45.2%.
  • a CsWO powder and a CsWO target were produced in the same manner as in Example 1 except for the above. Also, the obtained CsWO target was used in the film forming process.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the obtained transparent conductive film had transparency with a visible light transmittance of 69.6%, metallic conductivity with a specific resistance value of 1.3 ⁇ 10 ⁇ 3 ⁇ cm, and near-infrared reflection. It was found to be a transparent conductive film having a heat ray reflection performance of 40.9%.
  • the raw material composition was set to Rb 0.33 WO 3 (RbWO).
  • a blue RbWO powder and an RbWO target were produced in the same manner as in Example 1 except for the above points.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the obtained transparent conductive film has transparency with a visible light transmittance of 70.7%, metallic conductivity with a specific resistance of 3.1 ⁇ 10 ⁇ 4 ⁇ cm, and near-infrared reflection. It was found to be a transparent conductive film having a heat ray reflection performance of 55.3%.
  • the raw material composition was K 0.33 WO 3 (KWO).
  • KWO WO 3
  • a sky blue KWO powder and a KWO target were prepared in the same manner as in Example 1 except for the above points.
  • the obtained transparent conductive film contained alkali tungsten bronze, and the alkali tungsten bronze exhibited a hexagonal crystal in a powder X-ray diffraction pattern, and had no orthorhombic, trigonal, or pyrochlore phase shift.
  • the powder X-ray diffraction pattern of the alkali tungsten bronze the diffraction peaks of hexagonal (10-12) H and (20-20) H are divided into orthorhombic and trigonal crystals on the low angle side and on the high angle side. , it was confirmed that there was no surplus peak derived from the pyrochlore phase.
  • the obtained transparent conductive film had transparency with a visible light transmittance of 74.1%, metallic conductivity with a specific resistance value of 2.6 ⁇ 10 ⁇ 3 ⁇ cm, and near-infrared reflection. It was found to be a transparent conductive film having a heat ray reflection performance of 36.7%.
  • Example 2 In addition, in the film formation process, the method for removing moisture as in Example 1 was eliminated, and a normal sputtering film formation method was used. A transparent conductive film was formed in the same manner as in Example 1 except for the above points.
  • the water-cooled pipe on the outer wall of the chamber of the sputtering apparatus was exposed to the atmosphere without preliminary warm water heating.
  • the sheath heater and the substrate heater inside the chamber were not heated, and the temperature was reduced to room temperature.
  • the chamber was evacuated as it was, the ultimate vacuum was 6.5 ⁇ 10 ⁇ 4 Pa, which did not reach the 10 ⁇ 5 Pa level.
  • the water pressure in the chamber measured as it was without performing dummy sputtering was 5.0 ⁇ 10 ⁇ 4 Pa.
  • the shutter between the glass substrate and the target was opened, and the CsWO film was formed under the conditions of a sputtering gas pressure of 0.6 Pa and an input power of 600 W DC. was deposited to a thickness of 400 nm.
  • the obtained film was a near-infrared absorbing film with a visible light transmittance of 69.7% and a low solar transmittance of 46.3%. It was found that the film did not have metallic conductivity or infrared reflectivity and could not be called a transparent conductive film because it was as high as 0.9 ⁇ 10 4 ⁇ cm.
  • a blue (dark blue) CsWO powder and a CsWO target were produced in the same manner as in Example 1 except for the above.
  • Example 2 In the next film formation process, the device for removing moisture as in Example 1 was partly preserved and partly eliminated, and the sputter film was formed.
  • hot water of 60 ° C. is introduced into a water-cooled pipe that is stretched around the entire outer wall of the chamber of the sputtering device (manufactured by ULVAC, Inc., model number SBH2306) to heat it, and then nitrogen gas is introduced into the chamber to exhaust the moisture. While the chamber was vented to the atmosphere (preheat degassing).
  • the water pressure in the chamber was 4.0 ⁇ 10 ⁇ 4 Pa, which was measured as it was without performing dummy sputtering.
  • the shutter between the glass substrate and the target was opened, and the CsWO film was formed under the conditions of a sputtering gas pressure of 0.6 Pa and an input power of 600 W DC. was deposited to a thickness of 400 nm.
  • the obtained transparent conductive film was a near-infrared absorbing film with a visible light transmittance of 73.2% and a low solar transmittance of 46.4%, but near-infrared reflective.
  • the ratio is as low as 10.4%, and at the same time, the specific resistance value is as high as 4.6 ⁇ 10 6 ⁇ cm.
  • a blue (dark blue) CsWO powder and a CsWO target were produced in the same manner as in Example 1 except for the above.
  • Example 2 In the next film formation process, the method for removing moisture as in Example 1 was eliminated, and a normal sputtering film formation method was used.
  • the water cooling tube on the outer wall of the sputtering device chamber was not preheated with hot water, but was exposed to the atmosphere.
  • the sheath heater and the substrate heater inside the chamber were not heated, and the temperature was reduced to room temperature.
  • the chamber was evacuated as it was, the ultimate vacuum degree was 7.0 ⁇ 10 ⁇ 4 Pa, which did not reach the 10 ⁇ 5 Pa level.
  • the water pressure in the chamber measured without performing dummy sputtering was 6.0 ⁇ 10 ⁇ 4 Pa.
  • the shutter between the glass substrate and the target was opened, and the CsWO film was formed under the conditions of a sputtering gas pressure of 0.6 Pa and an input power of 600 W DC. was deposited to a thickness of 400 nm.
  • This film was a near-infrared absorbing film with a visible light transmittance of 62.5% and a low solar transmittance of 33.8%, but the near-infrared reflectance was as low as 8.6%. Since the specific resistance value was as high as 8.3 ⁇ 10 6 ⁇ cm, it was found that the film did not have metallic conductivity or infrared reflectivity and could not be called a transparent conductive film.

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