WO2022045028A1 - 近赤外線遮蔽膜、近赤外線遮蔽膜の製造方法 - Google Patents
近赤外線遮蔽膜、近赤外線遮蔽膜の製造方法 Download PDFInfo
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- WO2022045028A1 WO2022045028A1 PCT/JP2021/030695 JP2021030695W WO2022045028A1 WO 2022045028 A1 WO2022045028 A1 WO 2022045028A1 JP 2021030695 W JP2021030695 W JP 2021030695W WO 2022045028 A1 WO2022045028 A1 WO 2022045028A1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Definitions
- the present invention relates to a near-infrared shielding film and a method for manufacturing a near-infrared shielding film.
- the solar shielding film is required as one of the environmental measures to shield near infrared rays among the components of sunlight and prevent unnecessary heat from entering the room. Especially in window members for automobiles, the solar shielding film is becoming more and more important in terms of heat management associated with electrification.
- Patent Document 1 discloses a heat-retaining sheet in which a band-shaped film having infrared reflectivity and a band-shaped film having infrared absorption are knitted as warps or wefts, respectively. It is also disclosed that the band-shaped film having infrared reflectivity is a synthetic resin film subjected to aluminum vapor deposition processing.
- this type of light-shielding member is used, the appearance is half-mirror-like, so that the reflection is dazzling when used outdoors, and there is a problem in the landscape.
- Patent Document 2 discloses an infrared shielding material fine particle dispersion in which tungsten oxide particles and composite tungsten oxide particles are dispersed in a solid medium such as a resin, and it is also possible to impart an infrared shielding effect to a window material or the like. It has been disclosed.
- the dispersion in which composite tungsten oxide particles are dispersed is a material that exhibits excellent optical properties such as efficiently shielding sunlight, especially light in the near infrared region, and maintaining high transmittance in the visible light region.
- Patent Document 2 as a method for producing an infrared shielding material fine particle dispersion, infrared shielding material fine particles such as composite tungsten oxide fine particles are dispersed in an appropriate solvent to obtain a dispersion liquid, and a medium resin is added to the obtained dispersion liquid. It is also proposed to coat the surface of the substrate after the addition.
- Patent Document 3 includes a heat ray-shielding film in which a heat ray-shielding film containing a conductive oxide is formed on a substrate by a sputtering method or the like, and a protective film containing a silicon oxide and an alkali metal oxide is formed on the heat ray-shielding film.
- a method for producing a substrate is disclosed. Tin-containing indium oxide is also mentioned as the conductive oxide.
- the plasma frequencies of tin oxide and ITO are in the near-infrared light region, there is an advantage that transparency in a wide visible light region can be ensured, and infrared light having a wavelength longer than the plasma wavelength can be excluded by plasma reflection. It is also an advantage that the function is basically exhibited by a monolayer film except for a protective film for ensuring weather resistance.
- the free electron density contained in the transparent conductive film material such as tin oxide is lower than that of the metal, and the plasma wavelength is slightly longer, so that the shortest near-infrared ray having a strong sunlight intensity is not shielded. Therefore, although the film has a heat ray reflecting function, the solar radiation shielding function is at a level equal to or lower than that of the high-characteristic nanoparticles dispersion film.
- metal thin films such as Ag (silver) and Au (gold) strongly reflect infrared rays, but since the plasma frequency is in the visible light region, they are shielded from light depending on the wavelength of visible light. If it is left as it is, it will be strongly colored and become a dark film, but by forming a multilayer film that is alternately laminated with a colorless and high-refractive index dielectric thin film, effective near-infrared reflection rises using the interference effect of light. It is used by shifting the wavelength from the visible light region to the near infrared light region.
- Patent Document 4 discloses a technique of heat ray shielding glass in which a dielectric layer and a metal layer containing silver as a main component are laminated.
- the above-mentioned transparent conductor thin film and the multilayer film of metal and dielectric have high conductivity at the same time. Therefore, there is a problem that it reflects and interferes with communication radio waves and broadcasting radio waves having frequencies in the MHz to GHz band. In order to prevent such communication jamming, measures may be taken such as making a notch in a part of the radio wave reflector to enable communication.
- the radio wave reflectivity is based on the plasma reflection of free electrons in the near-infrared shielding material, it is based on a different principle from the transparent conductor thin film and the multilayer film of metal and dielectric. There was a need for an infrared shielding film.
- One aspect of the present invention is to provide a near-infrared ray shielding film having high heat ray shielding performance and excellent transparency of visible light and electromagnetic waves.
- a near-infrared shielding film composed of a continuous film of a cesium composite tungsten oxide represented by, wherein the continuous film contains one or more selected from orthorhombic, rhombohedral, and hexagonal crystals.
- the present invention it is possible to provide a near-infrared ray shielding film having high heat ray shielding performance and excellent transparency of visible light and electromagnetic waves.
- the flow chart of the manufacturing method of the near-infrared ray shielding film which concerns on embodiment of this invention.
- the XRD pattern of the near-infrared shielding film obtained in Example 1. Spectral characteristics of the near-infrared shielding film obtained in Example 1.
- Spectral characteristics of the near-infrared shielding film obtained in Example 2. The STEM-HAADF image of the near-infrared shielding film obtained in Example 2.
- the basic principle of near-infrared shielding in the near-infrared shielding film of the present embodiment is interband transition of bound electrons.
- the bound electron is an electron in which the surplus electrons generated in the cation due to the generation of oxygen defects are bound to the lattice points while locally distorting the ionic crystal lattice.
- the mode of movement in a solid with respect to an external voltage (potential potential) differs between bound electrons and free electrons.
- the bound electrons have a slower moving speed in the solid due to the external voltage than the free electrons. Therefore, when the strain of the lattice and the binding of electrons are strong, the conductivity of the thin film is greatly reduced.
- the bound electron absorbs an electromagnetic wave near the excitation energy and undergoes an electronic transition (inter-band transition). Therefore, the optical response of the thin film with bound electrons near the plasma wavelength is absorption rather than reflection.
- the band gap is around 3 eV, and the interband transition between the hybrid orbitals formed by the d orbital of the metal and the p orbital of the ligand (oxygen) is suppressed by the Fermi golden law. If so, large visible light transmission can be expected.
- the cesium composite tungsten oxide that is, the cesium polytang state material, which is one of the materials having the above characteristics, will be described in detail below.
- the near-infrared shielding film of the present embodiment is composed of a continuous film of cesium composite tungsten oxide as described above.
- the continuous film of the cesium composite tungsten oxide is referred to as a cesium polytang state film, and is hereinafter referred to as a CPT film. Further, the cesium composite tungsten oxide may be referred to as CPT.
- the CPT film constituting the near-infrared shielding film of the present embodiment contains cesium (Cs), tungsten (W), and oxygen (O) as main components, and is an orthorhombic crystal, a rhombohedral crystal, and a hexagonal crystal. Includes crystals with one or more crystal structures selected from.
- Crystal structures such as hexagonal crystals, cubic crystals, square crystals, orthorhombic crystals, and rhombohedral crystals, and amorphous structures are known as CPTs, but the CPT film constituting the near-infrared shielding film of the present embodiment is hexagonal. It has a crystal structure of crystals, orthorhombic crystals, and rhombohedral crystals.
- the CPT film may contain a crystal structure such as a cubic crystal, a tetragonal crystal other than a hexagonal crystal, an orthorhombic crystal, and a rhombohedral crystal, and an amorphous structure.
- the CPT constituting the CPT film is represented by the general formula Cs x W y Oz .
- Cs is an element necessary for maintaining a hexagonal, orthorhombic or rhombohedral lattice, and the phase separation of crystals can be suppressed by setting the Cs content to 4.8 atomic% or more. Further, by setting the Cs content to 14.6 atomic% or less, excellent spectral characteristics can be obtained.
- W is a basic element that expresses the excellent spectral characteristics of the CPT film, and by setting the W content ratio to 20.0 atomic% or more, the absorption of light in the near infrared light region can be enhanced. Further, by setting the W content ratio to 26.7 atomic% or less, the transmittance of light in the visible light region can be increased.
- O is an element that affects the optical absorption characteristics of the CPT film in terms of the balance with the W content ratio.
- z which indicates the content ratio of O, to the above range, it is possible to suppress phase separation of crystals and obtain a film having suitable near-infrared absorption characteristics.
- the CPT film included in the near-infrared shielding film of the present embodiment can be composed of a continuous film, specifically, a continuous thin film of polycrystals.
- the CPT film may contain voids and voids.
- (2) Crystal structure The crystal structure of CPT constituting the CPT film of the near-infrared shielding film of the present embodiment is a WO 6 octahedron (WO octahedron) formed of tungsten (W) and oxygen (O). Is the basic unit, and it is desirable that this is a hexagonal crystal arranged in hexagonal symmetry.
- the form is not limited to this, and generally speaking, it may be an orthorhombic crystal or a rhombohedral crystal due to the included lattice defects. That is, the continuous film included in the near-infrared shielding film of the present embodiment can include one or more selected from orthorhombic crystals, rhombohedral crystals, and hexagonal crystals. The continuous film included in the near-infrared shielding film of the present embodiment may be composed of only one or more selected from orthorhombic crystals, rhombohedral crystals, and hexagonal crystals.
- the orthorhombic CPT and the hexagonal CPT are (001) H // (001) R, (110) H // (100) R, (-110) H // (010) R (H).
- R represents a hexagonal crystal and an orthorhombic crystal, respectively, and the same applies hereinafter).
- the c-axis of the orthorhombic crystal is equal to the c-axis of the hexagonal crystal.
- the near-infrared shielding film of the present embodiment has an orthorhombic (010) R surface or a hexagonal prism surface [(100) H, (010) H, (110) H] and a bottom surface (001) H. At least a portion of one or more selected from and can have planar or linear lattice defects.
- At least a part of at least one of the hexagonal prism surfaces [(100) H, (010) H, (110) H] and the bottom surface (001) H is planar or planar.
- the axial lengths of the hexagonal a and b axes differ depending on the amount of lattice defects because the interatomic distance changes in the lattice defects. Therefore, it loses hexagonal symmetry and becomes orthorhombic.
- the crystal structure of the CPT film is basically a hexagonal crystal in which WO octahedrons are arranged hexagonally symmetrically, but if there are even a few lattice defects on the prism surface or the bottom surface, it is an orthorhombic crystal or an orthorhombic crystal. It should be described as a rhombohedral crystal.
- the near-infrared shielding film of the present embodiment can contain one or more types selected from tungsten deficiency and cesium deficiency as lattice defects.
- the CPT film can contain a tungsten defect as the most major defect.
- the CPT film which is the near-infrared shielding film of the present embodiment
- the CPT film is crystallized in the atmosphere or in a low-reducing atmosphere and heat-annealed over a sufficient period of time to bring it closer to the equilibrium phase
- it is brought close to the equilibrium phase at regular intervals on one prism surface.
- It has a structure in which tungsten defects are arranged.
- An example of such a tungsten deficiency is Cs 4 W 11 O 35 phase.
- the tungsten-deficient surface of the (010) R surface is arranged at a frequency of 8: 1 in the b-axis direction of the orthorhombic crystal.
- the CPT film of the present invention is not limited to such a form, and the embodiment of the tungsten deficiency differs depending on the Cs / W composition and the content ratio of O.
- a tungsten defect may exist over three types of prism surfaces, and this form may be used.
- Cs In order to express the tungsten deficiency, the general formula of CPT is expressed by Cs ⁇ W 1- ⁇ O 3- ⁇ , and the composition range of each of the above components is 0.2 ⁇ ⁇ ⁇ 0.54, 0 ⁇ ⁇ ⁇ 0. 115, 0 ⁇ ⁇ ⁇ 0.46. At this time, the maximum value of ⁇ indicating a tungsten deficiency is 0.115.
- Cs is a cation required for the hexagonal arrangement of the WO 6 octahedron, and ⁇ can be 0.2 ⁇ ⁇ ⁇ 0.54 as described above.
- the crystal structure of the orthorhombic, rhombohedral or hexagonal crystal of CPT is based on the WO6 octahedron formed of tungsten (W) and oxygen (O) as described above.
- a part of O of this WO 6 octahedron can be further randomly deleted by reduction. That is, one of the O of the WO 6 octahedron which constitutes one or more kinds of crystals selected from the orthorhombic crystal, the rhombohedral crystal, and the hexagonal crystal of CPT and is formed of tungsten (W) and oxygen (O).
- the parts can also be missing more randomly.
- the maximum value of ⁇ indicating an O deficiency in the above general formula is preferably 0.46. This is because when CPT is excessively reduced and oxygen is excessively deficient, the hexagonal WO 6 skeleton may be decomposed and WO 2 and metal W, which are lower oxides, may be deposited.
- N 2 gas and O 2 gas contain a small amount of water, and since adsorbed water is present on the wall of the reaction chamber where sputtering is performed, it is well known that water is taken into the film during film formation. Has been done.
- the hexagonal tunnel of the CPT crystal penetrates in the c-axis direction, and voids called hexagonal cavity and hexagonal window exist alternately.
- Cs is usually present in the hexagonal capacity, but since the hexagonal window site has excess voids through which oxygen and moisture can enter, it easily takes in the invading oxygen and moisture as described above, but its electronic influence is large. ..
- O 2- , OH- and OH 2 can also replace Cs with hexagonal cavities, and in this case also, the electrons in the conduction band decrease.
- the intrusion of O 2- , OH- , and OH 2 causes a decrease in electrons in the conduction band.
- the presence of protons and oxonium forms a structure lacking W and Cs in order to maintain a local charge balance in the crystal. That is, at least a part of the tungsten deficiency and the cesium deficiency in the CPT crystal is caused by one or more selected from O 2- , OH- and OH 2 that have invaded the hexagonal window site, the hexagonal cavity site, or the pyrochlore type void. It is occurring in.
- the hexagonal conversion lattice constant of CPT is not particularly limited, but it is preferable that the c-axis is 7.61 ⁇ ⁇ c ⁇ 7.73 ⁇ and the a-axis is 7.38 ⁇ ⁇ a ⁇ 7.53 ⁇ .
- hex 2 and patent geometry
- all hexagonal-equivalent lattice constants can be obtained by using these equations.
- a orth , birth, and coth in the above formula mean the lengths of the a-axis, b-axis, and c-axis of the orthorhombic crystal.
- a hex , b hex , and c hex mean the lengths of the a-axis, b-axis, and c-axis of the hexagonal crystal.
- a rhombom and ⁇ mean the lattice constant of the rhombohedral crystal and the angle between the axes.
- the lattice constant changes when the amount of electrons in the W-5d orbital at the lower part of the conduction band changes, affecting the pseudo Jahn-Teller strain of the WO 6 octahedron.
- the lattice constant also changes depending on the amount of tungsten deficiency and cesium deficiency. Therefore, by setting the lattice constant in the above range, for example, the amount of tungsten deficiency or cesium deficiency can be set in an appropriate range.
- (3) Optical characteristics The optical characteristics of the near-infrared shielding film of the present embodiment as a solar shielding film are not particularly limited, but ⁇ ⁇ 0.005VLT + 0.3 ( ⁇ : solar heat acquisition rate, VLT: visible light transmittance). It is preferable to satisfy.
- an appropriate CPT film as the near-infrared shielding film, it is possible to reduce the ⁇ value and obtain performance comparable to the characteristics of the ITO sputtered film and the resin multilayer heat ray reflecting film.
- the surface resistance value of the near-infrared shielding film of the present embodiment is not particularly limited, but can be 105 ⁇ / ⁇ or more.
- Such a surface resistance value can never be obtained with a metal multilayer film or an ITO sputtered film based on the principle of plasma reflection of free electrons.
- the surface resistance value is a characteristic obtained because the band-to-band transition of bound electrons existing in the CPT crystal is based on the near-infrared absorption principle.
- bound electrons are present in the lower part of the conduction band.
- the bound electrons are localized around W5 + cation, and the movement in the solid with respect to the external voltage (potential potential) is performed by electron hopping and tunneling effect, so the movement speed is generally extreme compared to free electrons. It will be late.
- the long-range interaction of localized electrons reduces the electron density of states at Fermi energy. This effect is called the Coulomb gap.
- the film thickness of the near-infrared shielding film of the present embodiment is not particularly limited, but is preferably 30 nm or more and 1200 nm or less. As described later, the near-infrared shielding film according to the present embodiment is a film obtained by sputtering film formation or the like, so that it is not necessary to use a dispersant or a medium resin, and it can be formed thinly and uniformly.
- the film thickness of the near-infrared shielding film of this embodiment By setting the film thickness of the near-infrared shielding film of this embodiment to 30 nm or more, the light absorption effect in the near-infrared light region can be sufficiently exhibited.
- the film thickness of the near-infrared ray shielding film of the present embodiment is 1200 nm or less, it is possible to suppress the coloring of the film while maintaining sufficient heat ray shielding performance.
- the amount of target used during manufacturing can be suppressed, the sputtering film formation time can be suppressed, and productivity can be improved.
- the near-infrared shielding film of the present embodiment can have optical characteristics in which the transmittance in the visible light region (wavelength 400 nm or more and 780 nm or less) is higher than the transmittance in the near-infrared light region (wavelength 780 nm or more and 1400 nm or less).
- the near-infrared shielding film of the present embodiment has a transmittance of 20% or less at a wavelength of 1400 nm when the transmittance at a wavelength of 550 nm is 50% or more. Further, when the transmittance of the near-infrared shielding film of the present embodiment is 30% or more and less than 50% at a wavelength of 550 nm, the transmittance at a wavelength of 1400 nm is 5% or less.
- the near-infrared shielding film of the present embodiment contains cesium containing one or more selected from oblique crystals, rhombohedral crystals, and hexagonal crystals within the range of the constituent ratios of the atoms of Cs, W, and O described above. If it is composed of a continuous film of composite tungsten oxide, the transmittance in the near-infrared light region can be made lower than the transmittance in the visible light region as described above even if the transmittance is arbitrary at a wavelength of 550 nm.
- the near-infrared shielding film described above can be produced by the method for producing a near-infrared shielding film according to the present embodiment. Therefore, some of the matters already described will be omitted.
- the method for manufacturing the near-infrared shielding film of the present embodiment can have the following steps as shown in the flow FIG. 10 of FIG.
- a heat treatment step (S2) in which the unheat-treated film is heat-treated at a temperature of 400 ° C. or higher and lower than 1000 ° C. to form a continuous film of cesium composite tungsten oxide.
- a sputtering method or a vacuum vapor deposition method can be used as the dry method.
- an unheat-treated film can be formed on a substrate by a sputtering method.
- the target used for forming the unheat-treated film is not particularly limited, but for example, the film can be formed using a cesium oxide tungsten oxide sintered body target.
- the composition of the target used when forming the unheat-treated film is, for example, Cs / W, which is the ratio of the amount of substance of cesium (Cs) contained and tungsten (W), to be 0.2 or more and 0.7 or less. Is preferable. This is because the composition of the target used at the time of film formation is reflected in Cs / W, which is the ratio of the amount of substance of cesium (Cs) and tungsten (W) contained in the film to be formed.
- the crystal structure of the target is not particularly limited because it does not directly affect the crystal structure of the film to be formed. Further, the target preferably has a relative density of 70% or more and a specific resistance of 1 ⁇ ⁇ cm or less.
- the method for producing the target described above is not particularly limited, but it can be produced, for example, by hot-press sintering the cesium composite tungsten oxide powder in a vacuum or in an inert atmosphere. This is because the sintered body manufactured in this manner has strength to withstand the machining in the target manufacturing and the brazing temperature at the time of bonding, and has conductivity capable of direct current sputtering.
- the sputtering method can be used as described above.
- the sputtering method the DC sputtering film forming method in which a DC voltage or a pulse voltage is applied to the target is preferable. This is because the film forming speed is high and the productivity is excellent.
- the base material on which the unheat-treated film is formed is not particularly limited, and for example, one or more selected from a transparent heat-resistant polymer film and glass can be used.
- glass is preferable as the base material. This is because the glass is transparent to light in the visible light region and does not deteriorate or deform in the heat treatment step S2 of the next step.
- the thickness of the glass is not particularly limited, and any thickness normally used for building window glass, automobile glass, display equipment, etc. can be used without particular limitation.
- the thickness of the glass is preferably 0.1 mm or more and 10 mm or less, for example.
- the sputter gas is not particularly limited, but for example, argon gas or a mixed gas of argon and oxygen can be used.
- argon gas or mixed gas in the film forming step can be selected according to the conditions of the heat treatment step S2 in the next step.
- the oxygen concentration is not particularly limited, but if the oxygen concentration in the mixed gas is high, the film forming rate decreases and the productivity decreases, so the oxygen concentration in the mixed gas is 20 vol%. It is preferably less than, and more preferably 5 vol% or more and 10 vol% or less.
- the purity of the argon gas is 99 vol% or more, and the oxygen concentration is preferably less than 1 vol%.
- the unheat-treated film obtained in the film forming step is usually amorphous, but a diffraction peak based on crystals may appear when X-ray diffraction measurement is performed. This is because a predetermined crystal structure such as a hexagonal crystal is formed again in the subsequent heat treatment step S2.
- the unheat-treated film obtained in the film forming step S1 can be heat-treated at a temperature of 400 ° C. or higher and lower than 1000 ° C. to form a continuous film of cesium composite tungsten oxide. .. Further, by heat-treating the unheat-treated film, a crystal structure containing one or more selected from orthorhombic crystals, rhombohedral crystals, and hexagonal crystals can be formed.
- the atmosphere can be selected and heat-treated according to the gas at the time of sputtering film formation so that the oxygen concentration in the CPT film is in an appropriate range.
- a gas containing oxygen can be used as the sputter gas in the film forming step S1, and for example, either the film forming step S1 or the heat treatment step S2 can be performed in an atmosphere containing oxygen. ..
- the heat treatment of the film in the heat treatment step S2 is 400 ° C. or more and less than 1000 ° C. in an inert gas atmosphere or a reducing atmosphere. It is preferable to carry out at temperature.
- nitrogen gas, argon gas, a mixed gas of hydrogen and nitrogen, a mixed gas of hydrogen and argon, or the like can be used as the inert gas atmosphere or the reducing atmosphere.
- the heat treatment step S2 is heat-treated in an oxidizing atmosphere such as air or oxygen, the oxidation of the film may proceed excessively. be.
- the oxygen vacancies in the CPT contained in the obtained CPT film are reduced, the crystal structure is changed to form an orthorhombic crystal or a rhombohedral crystal in which a large amount of tungsten deficiency and cesium deficiency are mixed, and electrons are generated in the lower part of the conduction band.
- the insulator may be deficient and the heat ray shielding performance may be deteriorated. Therefore, in this case, as described above, it is preferable to perform the heat treatment in the inert gas atmosphere or the reducing atmosphere.
- the obtained CPT film can be crystallized and defects can be arranged. Therefore, it has an appropriate band structure and electrons in the lower part of the conduction band, and has excellent heat ray shielding performance. An infrared shielding film is obtained.
- the crystal structure of oblique crystals, rhombohedral crystals, and hexagonal crystals maintains the structure even at a high temperature of 900 ° C or higher in an inert gas atmosphere or a reducing atmosphere, but when the heat treatment temperature is higher than 1000 ° C, CPT There is a risk that the CPT film will deteriorate due to the reaction between the film and the substrate, and that the film will disappear due to peeling. Further, at such a high temperature, there is a risk of deformation even when glass is used as the base material. Therefore, the heat treatment temperature is preferably less than 1000 ° C.
- the heat treatment time is not particularly limited, but the heat treatment time can be 10 minutes or more and 60 minutes or less because the formation of orthorhombic crystals, rhombohedral crystals, and hexagonal crystals proceeds rapidly.
- argon used as the sputtering gas in the film formation process
- a film is formed using only argon gas as the sputtering gas in the film forming step S1
- it is considered that the oxygen concentration of the film is appropriate or too low. Therefore, in the heat treatment step S2
- a CPT film having heat ray shielding performance can be obtained even if the heat treatment is performed in an atmosphere of an inert gas such as nitrogen gas containing no oxygen. Heat treatment with an inert gas such as nitrogen gas that does not contain oxygen can provide heat ray shielding performance over a wide temperature range.
- the unheat-treated membrane may be heat-treated in an oxidizing atmosphere containing oxygen in the heat treatment step.
- the heat treatment is performed in an oxidizing atmosphere containing oxygen, the oxygen concentration in the membrane can be maintained in a more appropriate range, and the heat ray shielding performance can be further improved. Therefore, in this case, in the heat treatment step S2, for example, the heat treatment may be performed in an oxygen-containing atmosphere having an oxygen concentration of 5 vol% or more and 20 vol% or less, and it is more preferable to select air as the heat treatment atmosphere, for example.
- the heat treatment furnace used does not have to have a special closed structure.
- the heat treatment temperature is preferably 400 ° C. or higher and 600 ° C. or lower.
- the heat treatment temperature is set to 400 ° C. or higher, the obtained CPT film is crystallized, and a near-infrared ray shielding film having excellent heat ray shielding performance can be obtained.
- the heat treatment temperature is set to 600 ° C. or lower, it is possible to suppress excessive oxidation of the obtained CPT film, for example, to make the amount of electrons in the lower part of the conduction band appropriate, and to improve the heat ray shielding performance.
- the heat treatment time is not particularly limited, but the heat treatment time can be 10 minutes or more and 60 minutes or less because the formation of orthorhombic crystals, rhombohedral crystals, and hexagonal crystals proceeds rapidly.
- the above-mentioned near-infrared shielding film can be obtained.
- the near-infrared shielding film obtained by the method for producing the near-infrared shielding film of the present embodiment can have the above-mentioned characteristics as a near-infrared shielding film.
- VLT Visible light transmittance
- ST25 solar transmittance
- SR25 solar reflectance
- ⁇ The solar heat gain rate ( ⁇ ) was calculated according to this.
- Precursors were made by drying in the air for hours. The precursor was heated to 800 ° C.
- the obtained CPT powder was put into a hot press device and sintered under the conditions of a vacuum atmosphere, a temperature of 950 ° C., and a pressing pressure of 250 kgf / cm 2 , to prepare a CPT sintered body.
- Cs / W which is the ratio of the amount of substance of cesium (Cs) and tungsten (W) contained, was 0.29.
- This CPT sintered body was machined to a diameter of 153 mm and a thickness of 5 mm, and bonded to a stainless steel backing plate using a metal indium brazing material to prepare a CPT target.
- the white CPT powder does not have an infrared shielding function unlike the composite tungsten oxide powder YM-01 and the like commercially available from Sumitomo Metal Mining.
- this CPT target was attached to a sputtering device (ULVAC, model number SBH2306), and an unheat-treated film having a film thickness of 400 nm was formed on a glass substrate (EXG, Corning, 0.7 mm thick).
- the sputtering was performed, the ultimate vacuum degree was set to 5 ⁇ 10 -3 Pa or less, and a mixed gas of 5 vol% oxygen / 95 vol% argon was used as the sputtering gas.
- the sputter gas pressure was set to 0.6 Pa, and the input power was set to DC 600 W.
- the sputter gas pressure was set to 0.6 Pa, and the input power was set to DC 600 W.
- the electromagnetic wave in the electromagnetic wave permeability in the present specification means an electromagnetic wave for various communications such as a communication radio wave and a broadcasting radio wave, and means, for example, an electromagnetic wave in the MHz and GHz bands.
- the film thickness of the CPT film was 396 nm.
- the transmission profile shown in FIG. 3A and the reflection profile shown in FIG. 3B were obtained.
- the transmittance and reflectance of the unheat-treated film before the heat treatment step are shown as "As deposited”.
- ⁇ 0.005VLT + 0.3 ⁇ ⁇ ⁇ (1)
- the CPT film obtained in this example shields light in the near-infrared light region having a shorter wavelength than that of the ITO film. It was also found that it has brighter and better solar shielding properties than the heat ray absorbing glass and the ATO fine particle dispersion film.
- STEM-HAADF observation From the obtained near-infrared shielding film, a thin cross-sectional sample was prepared using a focused ion beam (FIB) device, and a STEM-HAADF (scanning transmission electron electron) was used using a transmission electron microscope (Hitachi high-tech model: HF-2200). Z-contrast atomic image observation was performed in the microscope-high-angle scattered dark field image) mode. Since the HAADF image uses a diffracted wave at a high angle, the larger the atomic number, the stronger the atomic spot image can be obtained.
- FIG. 4 shows the observation results.
- Example 2 (Film formation process: S1) Using the CPT target prepared in Example 1, an unheat-treated film having a thickness of 400 nm was formed on a glass substrate under the same conditions as in Example 1 except that 10 vol% oxygen / 90 vol% argon gas was used as a sputtering gas. did. As a result of X-ray diffraction measurement of the obtained unheat-treated film, no diffraction peak was observed and it was amorphous. (Heat treatment step: S2) The unheat-treated membrane was put into the same lamp heating furnace as in Example 1 and heat-treated at 800 ° C. for 30 minutes in a nitrogen atmosphere.
- the film thickness of the CPT film was 405 nm.
- the transmission profile shown in FIG. 6A and the reflection profile shown in FIG. 6B were obtained.
- the transmittance and reflectance of the unheat-treated film before the heat treatment step are shown as "As deposited”.
- a thin cross-sectional sample was prepared using a focused ion beam (FIB) device, and a STEM-HAADF (scanning transmission electron electron) was used using a transmission electron microscope (Hitachi High-Tech model: HF-2200). Z-contrast atomic image observation was performed in the microscope-high-angle scattered dark field image) mode.
- FIG. 7 shows the observation results.
- the STEM-HAADF image of FIG. 7A is an observation of an atomic image of a hexagonal crystal from the [001] H direction. Since the HAADF image uses a diffracted wave at a high angle, the larger the atomic number, the stronger the atomic spot image can be obtained. Dark linear traces are observed in three directions, but these are traces of the hexagonal prism planes (100), (010), and (110), as shown in the selected area electron diffraction image of FIG. 7 (B). .. As shown in the atomic arrangement schematics attached to FIGS. 7 (A) and 7 (B), the hexagonal prism planes are arranged with Cs-W-Cs atomic planes and WOW atomic planes alternately.
- FIG. 7 (C) which is an enlarged view of the field of view
- FIGS. 7 (D), 7 (E), and FIG. 7 (E) respectively.
- FIG. 7 (F) it was found that W and Cs were dark and missing in the dark linear trace portion along (010) H. Further, it can be confirmed that the W and Cs defect planes are relatively regularly contained, and the structure is similar to that of the orthorhombic Cs 4 W 11 O 35 .
- Example 3 (Film formation process: S1) Using the CPT target prepared in Example 1, an unheat-treated film having a thickness of 400 nm was formed on a glass substrate under the same conditions as in Example 1 except that 0 vol% oxygen / 100 vol% argon gas was used as a sputtering gas. did.
- Heat treatment step: S2 The unheat-treated film was put into the same lamp heating furnace as in Example 1 and heat-treated at a temperature of 600 ° C. for 30 minutes in a nitrogen atmosphere.
- the film thickness of the CPT film was 405 nm.
- the transmission profile shown in FIG. 9A and the reflection profile shown in FIG. 9B were obtained.
- the transmittance and reflectance of the unheat-treated film before the heat treatment step are shown as "As deposited”.
- the near-infrared shielding film obtained in this example has high heat ray shielding performance by absorbing light in the infrared light region while maintaining sufficient transparency in the visible light region.
- the above values were plotted on the ⁇ -VLT graph shown in FIG. 12, it was confirmed that the values were lower than the above-mentioned equation (1). Therefore, it was found that the properties are much better than those of the commercially available heat ray absorbing film, and that the properties are the same as or higher than those of the ITO sputtered film.
- Example 4 (Film formation process: S1) Using the CPT target prepared in Example 1, an unheat-treated film having a thickness of 400 nm was formed on a glass substrate under the same conditions as in Example 1 except that 0 vol% oxygen / 100 vol% argon gas was used as a sputtering gas. did. As a result of X-ray diffraction measurement of the obtained unheat-treated film, no diffraction peak was observed and it was amorphous. (Heat treatment step: S2) The unheat-treated film was put into the same lamp heating furnace as in Example 1 and heat-treated in the air at 460 ° C. for 30 minutes.
- the film thickness of the CPT film was 398 nm.
- the transmission profile shown in FIG. 11A and the reflection profile shown in FIG. 11B were obtained.
- the transmittance and reflectance of the unheat-treated film before the heat treatment step are shown as "As deposited”.
- FIGS. 11A and 11B a profile is observed in which the main visible part having a wavelength in the range of 400 nm to 700 nm is largely transmitted, while all the light in the near infrared light region having a wavelength of 1000 nm or more is cut off. rice field.
- the reflection of light in the near-infrared light region is relatively large at the level of 30% to 40%, but the main body of light cut in the near-infrared light region is absorption. Therefore, it was found that this film absorbs the infrared region and has high heat ray shielding performance while maintaining sufficient transparency in the visible light region.
- “As deposited” in FIGS. 3A and 3B is the transmittance and reflectance of the obtained film.
- the transmittance of the obtained film with visible light having a wavelength of 550 nm exceeded 60%, but the transmittance of infrared rays having a wavelength of 1400 nm also exceeded 60%, so that the infrared rays were not shielded.
- the ratio of the transmittance at the wavelength of 1400 nm to the transmittance at the wavelength of 550 nm was as high as 1.00. Therefore, it was confirmed that there was almost no heat ray shielding performance.
- [XPS-w4f spectrum] In addition to the near-infrared shielding film prepared in Examples 1 to 3, Reference Example 1, Reference Example 2, and Cesium Tungsten Composite Oxide Powder were prepared, and the XPS-W4f spectrum was measured.
- the membrane of Reference Example 1 was prepared by the following procedure.
- Example 2 Using the CPT target prepared in Example 1, an unheat-treated film having a thickness of 400 nm was formed on a glass substrate under the same conditions as in Example 1 except that 10 vol% oxygen / 90 vol% argon gas was used as a sputtering gas. did.
- the obtained unheat-treated film was put into the same lamp heating furnace as in Example 1, and heat-treated at 540 ° C. for 30 minutes in an atmosphere of 1 vol% hydrogen and the balance of nitrogen.
- the membrane of Reference Example 2 was prepared by the following procedure.
- Example 2 Using the CPT target prepared in Example 1, an unheat-treated film having a thickness of 400 nm was formed on a glass substrate under the same conditions as in Example 1 except that 10 vol% oxygen / 90 vol% argon gas was used as a sputtering gas. did.
- the obtained unheat-treated film was put into the same lamp heating furnace as in Example 1 and heat-treated at 600 ° C. for 30 minutes in a nitrogen atmosphere.
- the precursor was prepared by mixing and kneading at 100 ° C. and drying in the air at 100 ° C. for 12 hours.
- the precursor was prepared by raising the temperature to 800 ° C. in an atmosphere of 1 vol% hydrogen and the balance of nitrogen, holding it for 1 hour, and then slowly cooling it to room temperature.
- the results are shown in FIG. 13A.
- the XPS-W4f spectrum of the sputtered film is composed of 4 peaks including the split doublet of the spin-orbit interaction of W 6+ and W 5+ , respectively, with W 6 + 7/2 as the maximum peak.
- W 6 + 7/2 the maximum peak.
- FIG. 13B Reference Example 2, Example 1, Example 2, Reference Example 1, and Example 3 are from the one with the smaller amount of W 5+ . It became the order.
- the composition of the O1s spectrum of CPT is as follows: first peak: OW 6+ (530.29 eV or more and 530.61 eV or less), second peak: OH and OW 5+ (531.47 eV) from the lowest binding energy. The peaks were separated on the assumption that the three groups were 531.76 eV or less) and the third peak: OH 2 (532.80 eV).
- FIG. 14B shows the area percentages of the second peak and the third peak. It can be seen that the second peak of the near-infrared shielding film increases in order of increasing conductivity of the film. That is, although the influence of OH is included in the second peak, the contribution of OW 5+ is superimposed, and it is considered that the increase is increased in descending order of W 5+ .
- Cs 4 W 11 O 35 which is an orthorhombic CPT powder shown as "CPT 800 ° C. 15 min” or “CPT 800 ° C. 60 min” in the figure, is placed in an atmosphere of 1 vol% H 2 and the balance is N 2 .
- the measurement results of the sample heated at 800 ° C. for 15 minutes or 60 minutes and reduced are also shown.
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Abstract
Description
本実施形態の近赤外線遮蔽膜は、一般式CsxWyOz(4.8≦x≦14.6、20.0≦y≦26.7、62.2≦z≦71.4、x+y+z=100)で表わされるセシウム複合タングステン酸化物の連続膜から構成される。そして、連続膜は斜方晶、菱面体晶、および六方晶から選択された1種類以上を含む。
(1)組成について
本実施形態の近赤外線遮蔽膜を構成するCPT膜は、セシウム(Cs)とタングステン(W)と酸素(O)を主成分とし、斜方晶、菱面体晶、および六方晶から選択された1種類以上の結晶構造の結晶を含む。
(2)結晶構造について
本実施形態の近赤外線遮蔽膜のCPT膜を構成するCPTの結晶構造は、タングステン(W)および酸素(O)により形成されたWO6八面体(W-O八面体)を基本ユニットとし、これが六方対称に配列した六方晶であることが望ましい。ただし、係る形態に限定されず、内包する格子欠陥により一般的に言えば斜方晶もしくは菱面体晶となっていてもよい。すなわち、本実施形態の近赤外線遮蔽膜が有する連続膜は斜方晶、菱面体晶、および六方晶から選択された1種類以上を含むことができる。なお、本実施形態の近赤外線遮蔽膜が有する連続膜は、斜方晶、菱面体晶、および六方晶から選択された1種類以上のみから構成することもできる。
(3)光学特性について
本実施形態の近赤外線遮蔽膜の日射遮蔽膜としての光学特性は特に限定されないが、η≦0.005VLT+0.3(η:日射熱取得率、VLT:可視光透過率)を満たすことが好ましい。
(4)表面抵抗値について
本実施形態の近赤外線遮蔽膜の表面抵抗値は特に限定されないが105Ω/□以上とすることができる。係る表面抵抗値は、自由電子のプラズマ反射を原理とする金属多層膜やITOスパッタ膜では決して得られない。係る表面抵抗値は、CPT結晶中に存在する束縛電子のバンド間遷移が近赤外線吸収原理となっているがゆえに得られる特性である。
(5)膜厚について
本実施形態の近赤外線遮蔽膜の膜厚は特に限定されないが、30nm以上1200nm以下であることが好ましい。本実施形態に係る近赤外線遮蔽膜は、後述するように、スパッタリング成膜等により得られる膜であるため、分散剤や媒体樹脂を使用する必要がなく、薄く均一に形成することができる。
[近赤外線遮蔽膜の製造方法]
次に、本実施形態の近赤外線遮蔽膜の製造方法について説明する。なお、本実施形態の近赤外線遮蔽膜の製造方法により、既述の近赤外線遮蔽膜を製造できる。このため、既に説明した事項の一部は説明を省略する。
(1)成膜工程
成膜工程S1では、スパッタリング法により、基材上に未熱処理膜を成膜できる。
(2)熱処理工程
次に、熱処理工程S2では、成膜工程S1で得られた未熱処理膜を400℃以上1000℃未満の温度で熱処理し、セシウム複合タングステン酸化物の連続膜とすることができる。また、未熱処理膜を熱処理することで、斜方晶、菱面体晶、および六方晶から選択された1種類以上を含む結晶構造を形成できる。
(成膜工程においてスパッタガスにアルゴンと酸素の混合ガスを用いた場合)
成膜工程S1で、スパッタガスにアルゴンと酸素の混合ガスを用いて成膜した場合、熱処理工程S2での膜の熱処理は、不活性ガス雰囲気または還元性雰囲気中で400℃以上1000℃未満の温度で行うことが好ましい。不活性ガス雰囲気または還元性雰囲気としては、窒素ガス、アルゴンガス、水素と窒素の混合ガス、水素とアルゴンの混合ガスなどを用いることができる。
(成膜工程においてスパッタガスにアルゴンのみを用いた場合)
成膜工程S1で、スパッタガスにアルゴンガスのみを用いて成膜した場合、膜の酸素濃度が適度または過少な状態と考えられる。このため、熱処理工程S2では、酸素を含まない窒素ガス等の不活性ガス雰囲気で熱処理を行っても熱線遮蔽性能を有するCPT膜が得られる。酸素を含まない窒素ガス等不活性ガスで熱処理すると、広い温度範囲で熱線遮蔽性能を得ることができる。
(評価方法)
以下の、各実施例、比較例における、評価方法について説明する。
(1)表面抵抗
得られた近赤外線遮蔽膜の表面抵抗は、三菱化学社製Loresta-GXおよびHiresta-UXを用いて測定した。
(2)膜厚
得られた近赤外線遮蔽膜の膜厚は、段差計(KLA-Tencor社製Alpha-Step IQ)を用いて測定した。
(3)X線回折パターン、格子定数
X線回折パターンはBRUKER AXS社のD2PHASERX線回折装置を用い、線源としてCu-Kα線を用いて測定した。結晶相の格子定数は、BRUKER AXS社の計算ソフトウェアDIFFRAC TOPASを用いて、空間群P63/mcmを仮定したPawley法で求めた。
(4)光学特性
得られた近赤外線遮蔽膜の光学特性は、分光光度計(日本分光株式会社製 V-670)を用いて透過率および8°入射拡散反射率を測定した。
[実施例1]
炭酸セシウム水溶液と三酸化タングステン水和物とを、含有するセシウム(Cs)とタングステン(W)との物質量の比がCs/W=0.33となる割合で混合・混練し、100℃12時間大気中で乾燥させて前駆体を作製した。前駆体を大気中800℃まで昇温して1時間保持した後、室温まで徐冷することで白いCPT粉末が得られた。得られたCPT粉末をホットプレス装置に投入し、真空雰囲気、温度950℃、押し圧250kgf/cm2の条件で焼結し、CPT焼結体を作製した。
(成膜工程:S1)
次に、このCPTターゲットをスパッタ装置(アルバック社製、型番SBH2306)に取り付け、ガラス基板(コーニング社製EXG、厚み0.7mm)の上に膜厚400nmの未熱処理膜を成膜した。なお、スパッタを行う際、到達真空度を5×10-3Pa以下とし、スパッタガスとして5vol%酸素/95vol%アルゴンの混合ガスを用いた。また、スパッタガス圧は0.6Pa、投入電力は直流600Wの条件とした。得られた未熱処理膜を、X線回折測定した結果、回折ピークは認められず非晶質であった。
(熱処理工程:S2)
未熱処理膜を、ランプ加熱炉(株式会社米倉製作所製、型番HP-2-9)に投入し、窒素雰囲気中、600℃で30分間熱処理した。
η=0.005VLT+0.3 ・・・ (1)
得られた近赤外線遮蔽膜は、熱線吸収膜であるにも関わらず、赤外線を反射するITOスパッタ膜の特性に近いことが図12より確認できる。これは図3A、図3Bに示したように、本実施例で得られたCPT膜が、ITO膜の場合よりも波長の短い近赤外光領域の光を遮蔽するからである。また熱線吸収ガラスや、ATO微粒子分散膜よりも、明るく優れた日射遮蔽特性をもつことが分かった。
(STEM-HAADF観察)
得られた近赤外線遮蔽膜から、集束イオンビーム(FIB)装置を用いて断面薄片試料を作製し、透過電子顕微鏡(日立ハイテク製 型式:HF-2200)を用いて、STEM-HAADF(走査透過電子顕微鏡-高角度散乱暗視野像)モードでZコントラスト原子像観察を行なった。HAADF像では高角度の回折波を用いるため原子番号が大きいほど強い原子スポット像が得られる。図4に観察結果を示す。
[実施例2]
(成膜工程:S1)
実施例1で作製したCPTターゲットを用いて、スパッタガスとして10vol%酸素/90vol%アルゴンガスを用いた点以外は実施例1と同じ条件でガラス基板上に膜厚400nmの未熱処理膜を成膜した。得られた未熱処理膜を、X線回折測定した結果、回折ピークは認められず非晶質であった。
(熱処理工程:S2)
未熱処理膜を、実施例1と同じランプ加熱炉に投入し、窒素雰囲気中、800℃で30分間熱処理した。
[実施例3]
(成膜工程:S1)
実施例1で作製したCPTターゲットを用いて、スパッタガスとして0vol%酸素/100vol%アルゴンガスを用いた点以外は実施例1と同じ条件でガラス基板上に膜厚400nmの未熱処理膜を成膜した。得られた未熱処理膜を、X線回折測定した結果、回折ピークは認められず非晶質であった。
(熱処理工程:S2)
未熱処理膜を、実施例1と同じランプ加熱炉に投入し、窒素雰囲気中、600℃の温度で30分間熱処理した。
[実施例4]
(成膜工程:S1)
実施例1で作製したCPTターゲットを用いて、スパッタガスとして0vol%酸素/100vol%アルゴンガスを用いた点以外は実施例1と同じ条件でガラス基板上に膜厚400nmの未熱処理膜を成膜した。得られた未熱処理膜を、X線回折測定した結果、回折ピークは認められず非晶質であった。
(熱処理工程:S2)
未熱処理膜を、実施例1と同じランプ加熱炉に投入し、大気中、460℃で30分間熱処理した。
[比較例1]
実施例1で作製したCPTターゲットを用いて、実施例1と同じ条件でガラス基板上に膜厚400nmの未熱処理膜を成膜した。ただし、熱処理工程は行わなかった。
[XPS-w4fスペクトル]
実施例1~3で作製した近赤外線遮蔽膜に加えて、参考例1、参考例2、およびセシウムタングステン複合酸化物粉を作製し、XPS-W4fスペクトルを測定した。
[XPS-O1sスペクトル]
XPS-W4fスペクトルの場合と同じ試料について、XPS-O1sスペクトルを測定した。結果を図14Aに示す。いずれの試料についてもXPS-O1sスペクトルは、高エネルギー側に裾野をもつことが観察された。
[XPS価電子帯観察]
実施例1と実施例2で得られた近赤外線遮蔽膜の価電子帯、および伝導帯下部をXPSで観察した。実施例1の結果を図15A、図15Cに、実施例2の結果を図15B、図15Dに示す。図15C、図15Dは、それぞれ図15A、図15Bの一部拡大図である。
Claims (15)
- 一般式CsxWyOz(4.8≦x≦14.6、20.0≦y≦26.7、62.2≦z≦71.4、x+y+z=100)で表わされるセシウム複合タングステン酸化物の連続膜から構成され、前記連続膜が斜方晶、菱面体晶、および六方晶から選択された1種類以上を含む近赤外線遮蔽膜。
- 前記斜方晶と前記六方晶とは、(001)H//(001)R、(110)H//(100)R、(-110)H//(010)R(HとRはそれぞれ六方晶と斜方晶を表わす)の格子対応で結ばれており、
前記斜方晶の(010)R面、または前記六方晶のプリズム面[(100)H、(010)H、(110)H]と底面(001)Hとから選択された1種類以上の少なくとも一部に面状または線状の格子欠陥を有する請求項1に記載の近赤外線遮蔽膜。 - 前記格子欠陥が、タングステン欠損およびセシウム欠損から選択された1種類以上を含む請求項2に記載の近赤外線遮蔽膜。
- 前記斜方晶、前記菱面体晶、および前記六方晶から選択された1種類以上の結晶を構成し、タングステン(W)および酸素(O)により形成されているW-O八面体のOの一部が、さらにランダムに欠損している請求項2または請求項3記載の近赤外線遮蔽膜。
- 前記斜方晶または前記六方晶の結晶中の六方トンネルの空隙、および前記菱面体晶の結晶中のパイロクロア型空隙から選択された1種類以上の空隙に過剰なO2-、OH-およびOH2から選択された1種類以上が配置されている請求項1から請求項4のいずれか1項に記載の近赤外線遮蔽膜。
- 前記セシウム複合タングステン酸化物の六方晶換算の格子定数が、7.61Å≦c≦7.73Å、7.38Å≦a≦7.53Åである請求項1から請求項5のいずれか1項に記載の近赤外線遮蔽膜。
- 光学特性が、η≦0.005VLT+0.3(η:日射熱取得率、VLT:可視光透過率)を満たす請求項1から請求項6のいずれか1項に記載の近赤外線遮蔽膜。
- 表面抵抗値が105Ω/□以上である請求項1から請求項7のいずれか1項に記載の近赤外線遮蔽膜。
- 膜厚が、30nm以上1200nm以下である請求項1から請求項8のいずれか1項に記載の近赤外線遮蔽膜。
- 基材上に乾式法により未熱処理膜を成膜する成膜工程と、
前記未熱処理膜を400℃以上1000℃未満の温度で熱処理し、セシウム複合タングステン酸化物の連続膜とする熱処理工程とを有し、
前記セシウム複合タングステン酸化物は、一般式CsxWyOz(4.8≦x≦14.6、20.0≦y≦26.7、62.2≦z≦71.4、x+y+z=100)で表わされ、
前記連続膜が斜方晶、菱面体晶、および六方晶から選択された1種類以上を含む近赤外線遮蔽膜の製造方法。 - 前記斜方晶と前記六方晶とは、(001)H//(001)R、(110)H//(100)R、(-110)H//(010)R(HとRはそれぞれ六方晶と斜方晶を表わす)の格子対応で結ばれており、
前記斜方晶の(010)R面、または前記六方晶のプリズム面[(100)H、(010)H、(110)H]と底面(001)Hとから選択された1種類以上の少なくとも一部に面状または線状の格子欠陥を有する請求項10に記載の近赤外線遮蔽膜の製造方法。 - 前記格子欠陥が、タングステン欠損およびセシウム欠損から選択された1種類以上を含む請求項11に記載の近赤外線遮蔽膜の製造方法。
- 前記斜方晶、前記菱面体晶、および前記六方晶から選択された1種類以上の結晶を構成し、タングステン(W)および酸素(O)により形成されているW-O八面体のOの一部が、さらにランダムに欠損している請求項11または請求項12記載の近赤外線遮蔽膜の製造方法。
- 前記斜方晶または前記六方晶の結晶中の六方トンネルの空隙、および前記菱面体晶の結晶中のパイロクロア型空隙から選択された1種類以上の空隙に過剰なO2-、OH-およびOH2から選択された1種類以上が配置されている請求項10から請求項13のいずれか1項に記載の近赤外線遮蔽膜の製造方法。
- 前記セシウム複合タングステン酸化物の六方晶換算の格子定数が、7.61Å≦c≦7.73Å、7.38Å≦a≦7.53Åである請求項10から請求項14のいずれか1項に記載の近赤外線遮蔽膜の製造方法。
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