Conductive oxide molecular films, conductive oxide molecular film aggregates, conductive films, conductors, and structures

Abstract

To provide a new conductive oxide molecular film containing tungsten.SOLUTION: A conductive oxide molecular film contains tungsten element.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] The present invention relates to conductive oxide molecular films, conductive oxide molecular film aggregates, conductive films, conductors, and structures. [Background technology]

[0002] Patent Document 1 discloses an infrared shielding material particle dispersion comprising infrared shielding material particle particles dispersed in a medium, wherein the infrared shielding material particle particles contain tungsten oxide particle particles and / or composite tungsten oxide particle particles, and the particle diameter of the infrared shielding material particle particles is 1 nm or more and / or 800 nm or less.

[0003] Patent Document 2 discloses a solar shading laminated structure comprising an intermediate layer containing fine particles having a solar shading function, interposed between two laminated plates selected from plate glass, plastic, and plastic containing fine particles having a solar shading function, characterized in that the fine particles having a solar shading function are composed of tungsten oxide fine particles and / or composite tungsten oxide fine particles.

[0004] Patent Document 3 describes a tungsten oxide and / or composite tungsten oxide having a maximum transmittance of 10% or more and less than 92% in the wavelength range of 400 nm to 780 nm, and a film surface resistance (sheet resistance) of 1.0 × 10⁻⁶. 10 A transparent conductive film is disclosed, characterized by having a density of Ω / □ or less. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2005 / 037932 [Patent Document 2] International Publication No. 2005 / 087680 [Patent Document 3] Japanese Patent Publication No. 2006-96656 [Non-patent literature]

[0006] [Non-Patent Document 1] ACS Nano 2020,14,15216 [Overview of the project] [Problems that the invention aims to solve]

[0007] As disclosed in Patent Documents 1 to 3, tungsten oxides and composite tungsten oxides are known to function as infrared shielding materials and transparent conductive films, and can be used in a variety of applications.

[0008] Furthermore, there was a need for new film-like materials using tungsten-containing oxides, with the aim of developing new functions and applying them to new uses.

[0009] Therefore, one aspect of the present invention aims to provide a novel conductive oxide molecular film containing tungsten. [Means for solving the problem]

[0010] In one aspect of the present invention, Contains tungsten-oxygen octahedron blocks, Mobility is 0.01cm 2 / (V·s) or more 1000cm 2 / (V·s) is less than or equal to The present invention provides conductive oxide molecular films. [Effects of the Invention]

[0011] One aspect of the present invention is that it is possible to provide a novel conductive oxide molecular film containing tungsten. [Brief explanation of the drawing]

[0012] [Figure 1]Figure 1 is an explanatory diagram of the crystal structure of hexagonal tungsten bronze, an example of a composite tungsten oxide. [Figure 2] Figure 2 is an explanatory diagram of the crystal structure of Cs4W11O35 and an example of the structure of a molecular film obtained from Cs4W11O35. [Figure 3] Figure 3 is an explanatory diagram of the crystal structure of Rb4W11O35 and an example of the structure of a molecular film obtained from Rb4W11O35. [Figure 4] Figure 4 is an explanatory diagram of the crystal structure of Cs6W11O36 and an example of the structure of a molecular film obtained from Cs6W11O36. [Figure 5] Figure 5 is an explanatory diagram of the crystal structure of Bi2W2O9 and an example of the structure of a molecular film obtained from Bi2W2O9. [Figure 6] Figure 6 is a schematic cross-sectional view of an example of the conductor of this embodiment. [Figure 7] Figure 7 is a schematic cross-sectional view of an example of the conductor of this embodiment. [Figure 8] Figure 8 is a schematic cross-sectional view of an example of the conductor of this embodiment. [Figure 9] Figure 9 is a schematic cross-sectional view of an example of the conductor of this embodiment. [Figure 10] Figure 10 is a schematic cross-sectional view of an example of the conductor of this embodiment. [Figure 11] Figure 11 is a schematic cross-sectional view of an example of the structure of this embodiment. [Figure 12] Figure 12 is a schematic cross-sectional view of an example of the structure of this embodiment. [Figure 13] Figure 13 is a schematic cross-sectional view of an example of the structure of this embodiment. [Figure 14] Figure 14 is a schematic cross-sectional view of an example of the structure of this embodiment. [Figure 15] Figure 15 is a schematic cross-sectional view of an example of the structure of this embodiment. [Modes for carrying out the invention]

[0013] The embodiments for carrying out the present invention will be described below with reference to the drawings, but the present invention is not limited to the embodiments described below, and various modifications and substitutions can be made to the embodiments described below without departing from the scope of the present invention. [Conductive oxide molecular films, conductive oxide molecular film aggregates] (1) Regarding the structure (1-1) Conductive oxide molecular film The conductive oxide molecular film of this embodiment (hereinafter also referred to as "molecular film") can contain tungsten. That is, the conductive oxide molecular film of this embodiment can contain tungsten as an element. As oxides of tungsten, composite tungsten oxides and tungsten oxides, which will be described later, are known and possess conductivity, so by making an oxide molecular film containing tungsten, conductivity can be achieved. Furthermore, since the above-mentioned composite tungsten oxides, etc., have excellent light transmittance (transparency) in the visible light region, they can also be made into transparent conductive oxide molecular films.

[0014] In particular, the conductive oxide molecular film of this embodiment preferably contains tungsten-oxygen octahedron blocks. While the molecular film of this embodiment may consist solely of tungsten-oxygen octahedron blocks, this does not eliminate the possibility of unavoidable impurities being introduced during the manufacturing process.

[0015] The molecular film of this embodiment and the tungsten-oxygen octahedron blocks contained within the molecular film will be described with reference to Figure 1, which is a schematic plan view.

[0016] Figure 1 shows the crystal structure of hexagonal tungsten bronze having multiple tungsten-oxygen octahedral blocks 11 formed from WO6 units. The tungsten-oxygen octahedral block 11 has a structure in which oxygen is placed at the vertices of the octahedron and tungsten is placed at the center of the octahedron. The molecular film of this embodiment can contain multiple tungsten-oxygen octahedral blocks 11, as shown in Figure 1, for example, and multiple tungsten-oxygen octahedral blocks 11 can be arranged, for example, in a planar or linear manner.

[0017] The molecular film of this embodiment can also have, for example, a structure with a repeating structure of tungsten-oxygen octahedron blocks as a basic skeleton.

[0018] As will be described later, the molecular film of this embodiment can also contain a composite tungsten oxide. In this case, the composite tungsten oxide, for example, has a structure in which six of the above-mentioned tungsten-oxygen octahedron blocks 11 aggregate to form a hexagonal void 12, and M13 contained in the composite tungsten oxide is arranged in the void 12 to form one unit, and a structure in which a large number of these units aggregate can be formed.

[0019] For example, Fig. 2(B) shows an example of the structure of the molecular film obtained from Cs4W shown in Fig. 2(A). 11 O 35 Fig. 2(B) corresponds to the structure of the molecular film obtained in Examples 2 to 4 described later, for example.

[0020] Also, Fig. 3(B) shows an example of the structure of the molecular film obtained from Rb4W shown in Fig. 3(A). 11 O 35 Fig. 3(B) corresponds to the structure of the molecular film obtained in Example 5 described later, for example. Figs. 2(B) and 3(B) have a structure in which M13 is arranged in the hexagonal void 12 as described above. In the case of Fig. 2(B), M13 is Cs, and in the case of Fig. 3(B), M13 is Rb.

[0021] On the other hand, for example, Fig. 4(B) shows an example of the structure of the molecular film obtained from Cs6W shown in Fig. 4(A). 11 O 36 The structure of the molecular film shown in Fig. 4(B) has, for example, the same pyrochlore structure as CsW2O6. Note that Cs 8.5 W 15 O 48The molecular films obtained from this also have a similar structure. Locally, these have a structure in which M13 is arranged in the hexagonal voids formed by the tungsten-oxygen octahedron block 11, but the hexagons and M are stacked in the direction perpendicular to the bc plane while shifting in the c-axis direction as shown in Figure 4(B). Figure 4(B) corresponds to the structure of the molecular film obtained in Example 1, which will be described later.

[0022] Furthermore, the molecular film of this embodiment may also contain tungsten oxide, in which case the tungsten oxide can be formed from the tungsten-oxygen octahedron block or the like. As a corresponding structure, for example, Figure 5(B) shows an example of the structure of a molecular film obtained from Bi2W2O9 shown in Figure 5(A). Figure 5(B) corresponds to the structure of the molecular film obtained in Example 6, which will be described later.

[0023] The molecular film of this embodiment can be made conductive as described above by containing the element tungsten. Furthermore, the molecular film of this embodiment can be made highly conductive by including a tungsten-oxygen octahedron block. In addition, by introducing oxygen vacancies into the tungsten-oxygen octahedron block, a molecular film with particularly excellent conductivity can be made.

[0024] Furthermore, since the molecular film of this embodiment has a sheet shape, it can exhibit high conductivity even with a thin film thickness. Moreover, the molecular film of this embodiment can suppress visible light scattering and is capable of producing a molecular film with excellent visible light transparency.

[0025] The molecular film in this embodiment may be crystalline or amorphous.

[0026] The molecular film of this embodiment can be manufactured, as described later, by using, for example, a composite tungsten oxide having a layered crystalline structure as a raw material and exfoliating it down to a single layer, which is the basic smallest unit of the crystalline structure, through soft chemical treatment. The molecular film of this embodiment can have a sheet shape with a thickness of approximately 1 nm to 10 nm (corresponding to several to tens of atoms). Depending on the conditions of the soft chemical treatment, the molecular film of this embodiment can also be exfoliated into two layers, three layers, or more, and manufactured using these films.

[0027] As will be described later, multiple molecular films of this embodiment can be assembled to form a molecular film aggregate.

[0028] By adjusting the synthesis (calcination) temperature of composite tungsten oxides having a layered crystalline structure before exfoliation through soft chemical treatment, or by utilizing single crystals of composite tungsten oxides or tungsten oxides, the longitudinal length of the molecular film can be controlled. For example, it is possible to synthesize molecular films with longitudinal lengths adjusted within a range of 20 nm to 1 mm. Even molecular films with varying longitudinal lengths can exhibit excellent conductivity. Therefore, molecular film assemblies of this embodiment, including the molecular film, can be applied, for example, as electrodes or electrical circuits.

[0029] Molecular films are flexible and may have a curved sheet shape in liquids, for example. Their flexibility is maintained even in solids; for instance, they can be bent together with a flexible substrate, and even when bent, the atomic arrangement and other structural elements within the molecular film remain intact.

[0030] From the viewpoint of ensuring visible light transparency, the molecular film is preferably 200 nm or less in thickness, more preferably 100 nm or less, even more preferably 50 nm or less, and even more preferably 10 nm or less. (1-2) Conductive oxide molecular film aggregate Multiple molecular films of this embodiment can be assembled to form a conductive oxide molecular film aggregate (hereinafter also referred to as a "molecular film aggregate"). In other words, a molecular film aggregate can contain molecular films.

[0031] The molecular film aggregate of this embodiment can be composed solely of molecular films, or it can be composed of a laminate of molecular films, etc. Furthermore, the molecular films may be in contact with each other or may be separated. In other words, although the term "assembly" is used for convenience, the molecular films do not necessarily have to be in contact with each other. The molecular film aggregate of this embodiment can be constructed by laying molecular films on a smooth substrate, or it can be constructed by combining lamination and laying.

[0032] In this embodiment, the molecular film aggregate can be made to have an area suitable for the application by arranging multiple molecular films in a tiled manner on the same plane.

[0033] In molecular film assemblies, molecular films can be arranged without gaps, but gaps may also be present between the molecular films.

[0034] The molecular film aggregate of this embodiment can be manufactured, for example, by stacking or arranging molecular films on a smooth substrate. Alternatively, the molecular film aggregate of this embodiment can also be obtained by heat treatment after stacking or arranging molecular films on a smooth substrate. In this case, from the viewpoint of introducing oxygen vacancies into the tungsten-oxygen octahedral blocks of the molecular film and exhibiting particularly excellent conductive performance, it is preferable to perform the heat treatment in an inert gas atmosphere, a vacuum atmosphere, or a reducing atmosphere, and more preferably in a reducing atmosphere.

[0035] The molecular film of the molecular film aggregate of this embodiment may contain tungsten, as described above, and it is particularly preferable that it contains tungsten-oxygen octahedral blocks. Furthermore, it is preferable that the molecular film of the molecular film aggregate of this embodiment has a repeating structure of the said blocks as its basic framework. That is, it is preferable that it is crystalline. The fact that the repeating structure of tungsten-oxygen octahedral blocks is the basic framework can be confirmed by analyzing the electron diffraction pattern measured by a transmission electron microscope or by analyzing the XRD pattern measured by an X-ray diffraction (XRD) device.

[0036] When measuring the structure of molecular films and molecular film assemblies in this embodiment using an X-ray diffractometer, the molecular films and molecular film assemblies may be in the form of sheets with a thickness of approximately 1 nm to 10 nm. Therefore, it is necessary to measure the XRD pattern using thin-film X-ray diffraction rather than powder X-ray diffraction. In thin-film X-ray diffraction, the incident angle of the X-rays is fixed to a small angle of 0.5° or less near the critical angle of total internal reflection. As a result, the penetration depth of the X-rays into the sample is several tens of nm, and the diffracted X-ray signal can be detected with high accuracy with almost no influence from the substrate. Thin-film X-ray diffraction methods include grazing incidence X-ray diffraction (GI-XRD) and in-plane X-ray diffraction, but in-plane X-ray diffraction is preferred. In-plane X-ray diffraction is also called the φ-2θχ scan method, and because the goniometer scans horizontally within the sample plane, it is important to accurately adjust the axis of tilt and tilt of the sample within the plane. As a result, the angle of the incident X-rays can be controlled to 0.2° or less, making it possible to measure the crystalline state of ultrathin films with a thickness of a few nanometers or less, as well as the orientation of crystal planes perpendicular to the substrate surface. Examples of equipment capable of performing measurements using in-plane X-ray diffraction include Rigaku's fully automated multi-purpose X-ray diffractometer, SmartLab. (2) Regarding composition The molecular film of this embodiment is a molecular film of an oxide containing the element tungsten. Preferably, the molecular film of this embodiment contains one or more types selected from composite tungsten oxides and tungsten oxides.

[0037] The following describes composite tungsten oxides and tungsten oxides that can be suitably contained in the molecular film of this embodiment. (Composite tungsten oxide) Tungsten oxide (WO3) is not effective as a conductive material because it does not contain any useful free electrons.

[0038] On the other hand, WO has an oxygen deficiency. 3-δ Furthermore, composite tungsten oxides, such as those obtained by adding positive elements like Na to WO3, are known to be conductive materials and possess free electrons. Analysis of single crystals of these free-electron materials suggests the response of free electrons to infrared light.

[0039] By adding M, an element or atomic group (molecule) described later, to the aforementioned WO3, a composite tungsten oxide is formed, generating free electrons in the WO3, making it effective as a conductive material. Furthermore, introducing oxygen vacancies results in particularly excellent conductive properties.

[0040] In other words, by controlling the amount of oxygen in the WO3 and adding M, which generates free electrons, a highly conductive material can be obtained. For this reason, the molecular film of this embodiment preferably contains the above-mentioned composite tungsten oxide. The general formula for this composite tungsten oxide obtained by controlling the amount of oxygen and adding M, which generates free electrons, is given by M. x W y O zWhen written as above, it is preferable that x, y, and z satisfy the relationships 0.001 ≤ x / y ≤ 1 and 2.0 ≤ z / y ≤ 3.5. However, M in the above general formula can be one or more selected from the group of elements and the group of atomic groups. The above group of elements includes H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, As, Sb, Bi, S, Se, Te, F, Cl, Br, and I. The above group of atomic groups includes Bi₂O₂, OH, H₂O, H₃O, and NH₄. In the above general formula, W represents tungsten and O represents oxygen. The molecular film of this embodiment may also contain a composite tungsten oxide, as described above. In this case, it is preferable that the composite tungsten oxide contained in the molecular film satisfies the above general formula.

[0041] First, let's explain the x / y values ​​that indicate the amount of M added.

[0042] If the x / y value is 0.001 or greater, a sufficient amount of free electrons are generated in the composite tungsten oxide, and the desired conductivity can be obtained. Furthermore, as the amount of M added increases, the supply of free electrons increases, and the conductivity also improves, but this effect saturates when the x / y value is around 1. Also, if the x / y value is 1 or less, it is preferable because the generation of impurity phases can be suppressed.

[0043] Next, we will explain the value of z / y that indicates the control of oxygen quantity. General formula W y O z In the case of tungsten oxides, by making z / y less than 3, free electrons can be generated due to oxygen vacancies. Therefore, in the case of tungsten oxides, conductive properties can be achieved by making z / y less than 3.

[0044] In contrast, the general formula M xW y O z In the composite tungsten oxide represented by the above general formula W y O z In addition to the same mechanism as that used for tungsten oxides, even when z / y ≤ 3.5, there is a supply of free electrons due to the amount of M added as described above. Furthermore, in molecular films, the surface may be negatively charged, so conductive properties may be exhibited even when z / y is 3.5 due to the supply of free electrons. However, the crystalline phase of WO2 may reduce the conductive properties. Therefore, from the viewpoint of suppressing the formation of WO2, it is preferable that z / y be 2.0 or higher. From the above, 2.0 ≤ z / y ≤ 3.5 is preferred, more preferably 2.2 ≤ z / y ≤ 3.3, and even more preferably 2.45 ≤ z / y ≤ 3.3.

[0045] Here, M is added to the M x W y O z From the standpoint of stability, it is even more preferable that M contains one or more selected from H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Fe, Cu, Ag, In, Tl, Sn, Pb, and Yb.

[0046] The crystal structure of the composite tungsten oxide is not particularly limited and can have one or more structures selected from, for example, hexagonal, cubic, or tetragonal crystals. Furthermore, the composite tungsten oxide may be amorphous.

[0047] The composite tungsten oxide in the molecular film of this embodiment can have, for example, the atomic configuration shown in Figure 1.

[0048] As described above, six tungsten-oxygen octahedral blocks 11 are assembled to form a hexagonal void 12, and M13 containing the composite tungsten oxide is placed in the void 12 to form a single unit, and many such units can be assembled. Such unit structures may be arranged regularly or randomly in the molecular film of this embodiment. The molecular film of this embodiment, by including such a structure, has particularly improved conductivity and light transmission in the visible light region.

[0049] When the above-mentioned M is added to the hexagonal voids, light transmission in the visible light region is particularly improved, and the conductive properties are particularly enhanced. Generally, when M has a large ionic radius or molecular size (atomic group size), the unit structure shown in Figure 1 is more likely to be formed. Specifically, when M contains one or more elements selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, the unit structure shown in Figure 1 is more likely to be formed. For this reason, it is preferable that the composite tungsten oxide contains one or more elements selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn as M. Note that M can also be composed of one or more elements selected from the above group of elements.

[0050] Furthermore, in composite tungsten oxides containing one or more elements selected from Cs and Rb among these elements with large ionic radii, the unit structure shown in Figure 1 is easily formed, exhibiting excellent conductivity and particularly high performance. For this reason, it is more preferable for M to contain one or more elements selected from Cs and Rb. Note that M can also be composed of one or more elements selected from Cs and Rb.

[0051] Of course, even if M includes elements or atomic groups other than those mentioned above, it is sufficient as long as M exists in the hexagonal void formed by the WO6 unit; it is not limited to the elements mentioned above.

[0052] When the composite tungsten oxide having the above structure has a uniform crystalline structure, the amount of M added is preferably 0.001 ≤ x / y ≤ 1 in terms of the x / y value, and more preferably 0.2 ≤ x / y ≤ 0.6. (Tungsten oxide) The molecular film of this embodiment may also contain tungsten oxide. Tungsten oxide has the general formula W y O z (However, W is tungsten, O is oxygen, and 2.0 ≤ z / y < 3.5) is used as the general formula for W. y O zIn the tungsten oxide expressed as, the composition range of tungsten and oxygen is preferably such that the ratio of oxygen to tungsten (z / y) is less than 3.5, more preferably 2.0 ≤ z / y < 3.5, even more preferably 2.2 ≤ z / y < 3.5, and particularly preferably 2.45 ≤ z / y ≤ 3.499.

[0053] If the z / y value is 2.0 or higher, it is possible to avoid the appearance of an unintended WO2 phase in the tungsten oxide and to improve the chemical stability of the material, making it a particularly effective conductive oxide molecular film. Furthermore, by setting the z / y value to preferably less than 3.5, and more preferably 3.499 or lower, a particularly sufficient amount of free electrons are generated due to oxygen vacancies to improve conductivity, resulting in an efficient conductive material. Here, in the case of a molecular film, the surface may be negatively charged, so z / y may exceed 3. However, in the case of z / y = 3.5, there may be no oxygen vacancies in the tungsten oxide molecular film, and a sufficient amount of free electrons may not be generated, resulting in the inability to obtain the desired sufficient conductivity.

[0054] Furthermore, the so-called "Magnelli phase," which has a composition ratio expressed as 2.45 ≤ z / y ≤ 3.499, is chemically stable and exhibits excellent light absorption and reflection properties in the near-infrared region, making it more preferable to use it as an infrared absorbing material. For this reason, the z / y value is even more preferably 2.45 ≤ z / y ≤ 3.499, as described above. Note that the above range of z / y values ​​also takes into account the case where the molecular film surface is negatively charged, as previously mentioned. (3) Characteristics of molecular films and molecular film assemblies The molecular film of this embodiment can also have chromic properties. Tungsten oxides and composite tungsten oxides, like other hydrated tungsten oxides, are known to be both photochromic and electrochromic materials. The molecular film of this embodiment is also a photochromic and electrochromic material. The molecular film of this embodiment exhibits a photochromic reaction in response to high-energy light such as ultraviolet and visible light. Furthermore, if the energy threshold required for the reaction is low, it also exhibits a photochromic reaction in response to infrared light. In response to ultraviolet and visible light, cationic species such as protons generated around the molecular film are adsorbed onto the molecular film, creating a light absorption and reflection region. Therefore, in photochromic materials, it is important to increase the surface area so that a large amount of cationic species can be adsorbed. It is also important to increase the crystallinity so that the generation of the light absorption region due to the adsorption of cationic species can be further increased. Organic substances can be used as sources of protons in response to ultraviolet and visible light. Examples of sources for these protons include bulky guests such as quaternary ammonium ions used in the soft chemical treatment described later, and resins used as the matrix of the structure.

[0055] As described above, the molecular film and molecular film aggregate of this embodiment have excellent conductivity and can therefore be used in various applications where conductivity is required, such as electrodes and electrical circuits.

[0056] The electrical properties of the molecular film and molecular film aggregate in this embodiment are not particularly limited, but the mobility is 0.01 cm. 2 / (V·s) or more 1000cm 2 It is preferable that it is less than or equal to / (V·s), and 1 cm 2 / (V·s) or more 500cm 2 It is more preferable that it be less than or equal to (V·s).

[0057] Furthermore, the molecular film and molecular film aggregate of this embodiment have a carrier density of 1.0 × 10⁻⁶ 19 / cm 3 The above 1.0 × 10 24 / cm 3 Preferably, it is 1.0 × 10 20 / cm 3 The above 1.0 × 10 23 / cm 3 The following is more preferable:

[0058] In this embodiment, the molecular film and molecular film aggregate preferably satisfy the above-mentioned preferred range for either mobility or carrier density, and more preferably satisfy the above-mentioned preferred range for both.

[0059] Furthermore, the molecular film and molecular film aggregate of this embodiment preferably have an average thickness of crystallites of 2 nm or more, more preferably between 5 nm and 100 nm, and even more preferably between 10 nm and 50 nm. By setting the average thickness of crystallites of the molecular film and molecular film aggregate of this embodiment to 2 nm or more, the conductive properties can be particularly enhanced.

[0060] Furthermore, by selecting the crystal size of the composite tungsten oxide with a layered crystalline structure before exfoliation used as a raw material, and the heat treatment conditions when manufacturing molecular film aggregates, the average thickness of the crystallites can be easily brought within the above-mentioned range.

[0061] The average crystallite thickness can be calculated from images obtained by observing a cross-section of a molecular film or molecular film aggregate along its thickness direction using a transmission electron microscope (TEM). The average crystallite thickness is the average of the crystallite thicknesses along the thickness direction of the molecular film, etc., measured at multiple measurement points separated from each other by 20 nm to 100 nm in the observation image. The number of measurement points is not particularly limited, but it is preferable to have, for example, 5 to 20 points. [Method for manufacturing molecular films] Next, the method for manufacturing the molecular film according to this embodiment will be described. Since the molecular film described above can be manufactured according to the method for manufacturing the molecular film according to this embodiment, the matters already explained will be omitted from further explanation.

[0062] In the method for producing molecular films according to this embodiment, for example, a composite tungsten oxide having a layered crystalline structure can be used as a raw material. The raw material having a layered crystalline structure can be exfoliated to one or more layers, which are the basic smallest units of the crystalline structure, by soft chemical treatment, and a molecular film can be obtained. Furthermore, by reduction treatment, a molecular film with excellent conductive properties can be obtained.

[0063] Soft chemical treatment is a process that combines acid treatment and colloidalization treatment. Specifically, when a composite tungsten oxide powder having a layered crystalline structure is brought into contact with an acidic aqueous solution such as hydrochloric acid, the product is filtered, washed, and dried. Some or all of the alkali metal ions that were present between the layers before the acid treatment are replaced with hydrogen ions, and a hydrogen-type substance is obtained. Next, when the obtained hydrogen-type substance is placed in an aqueous solution such as an amine and stirred, it becomes colloidal. At this time, the layers that made up the layered crystalline structure are peeled off into individual layers. Specifically, the layers that made up the layered crystalline structure are oxides containing the element tungsten, and for example, those with a repeating structure of tungsten-oxygen octahedron blocks as the basic framework.

[0064] Therefore, the method for producing the molecular film according to this embodiment may include the following acid treatment step and colloidization step. Since the acid treatment step and colloidization step can prepare the molecular film for use as raw material before the heat treatment step, the two steps together can also be called the molecular film preparation step for raw material.

[0065] In the acid treatment process, a raw material having a layered crystalline structure is brought into contact with an acidic aqueous solution, and the product is washed and dried to obtain a hydrogen-type substance.

[0066] In the colloidalization process, a hydrogen-type substance is mixed with a liquid containing a bulky guest to obtain a molecular film.

[0067] As a raw material having a layered crystalline structure, for example, a composite tungsten oxide can be used. This raw material is Rb4W 11 O 35 , Cs4W11 O 35 , Cs 6+A W 11 O 36 (0≦A≦0.31), Cs 8+B W 15 O 48 It is preferable that the composite tungsten oxide contains one or more types selected from (0≦B≦0.5) and (Bi₂O₂)W₂O₃. These composite tungsten oxides have alkali metal ions such as Rb and Cs, and cations such as Bi₂O₂ between the layers.

[0068] In soft chemical processing, for example, a composite tungsten oxide powder having a layered crystalline structure is brought into contact with an acidic aqueous solution to obtain a hydrogen-type substance. Specifically, for example, Rb 4-a H a W 11 O 35 (0≦a≦4), Cs 4-b H b W 11 O 35 (0≦b≦4), Cs 6+A-c H c W 11 O 36 (0≦c≦6.31), Cs 8+B-d H d W 15 O 48 (0≦d≦8.5), (Bi2O2) 1-e H 2e A hydrogen-type substance of W2O7 (0 ≤ e ≤ 1) is obtained. These hydrogen-type substances are obtained in which some or all of the alkali metal ions and cations present between the layers before acid treatment have been replaced with hydrogen ions. The hydrogen-type substance exists as a hydrate in aqueous solution and retains its hydrate even after filtration, washing, and drying, when air-dried at room temperature. It is also possible to obtain a substance in which hydrogen H is replaced with oxonium.

[0069] The acidic aqueous solution used in the acid treatment is not particularly limited as long as it does not dissolve the complex tungsten oxide; hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, etc., can be used. The amount of ion exchange can be changed depending on the type and concentration of the acid and the number of treatments.

[0070] Next, by inserting a bulky guest between layers of a hydrogen-type material, such as an acid-treated product, the hydrogen-type material can be exfoliated down to a single layer, which is the smallest basic unit of the crystalline structure, thereby obtaining a sheet-shaped molecular film. Specifically, for example, Rb 4-a W 11 O 35 a- (0≦a≦4), Cs 4-b W 11 O 35 b- (0≦b≦4), Cs 6+A-c W 11 O 36 c- (0≦c≦6.31), Cs 8+B-d W 15 O 48 d- (0≦d≦8.5), (Bi2O2) 1-e W2O7 e- A molecular film with (0 ≤ e ≤ 1) can be obtained. Here, if the molecular film is strictly separated, it is obtained in a state where all parts are negatively charged, but because bulky guests modify the molecular film surface as cations, the overall state including the bulky guests is considered to be close to neutral.

[0071] Bulky guests, such as quaternary ammonium ions, are used by contacting them with hydrogen-type substances in a liquid such as water or an organic solvent. For example, a material supplying a bulky guest, such as a quaternary ammonium salt, can be dissolved in a suitable liquid, and the hydrogen-type substance can be added thereto. By mixing and shaking the liquid, the hydrogen-type substance can be detached down to a single layer.

[0072] As the bulky guest ion, one or more quaternary ammonium ions selected from tetrabutylammonium ions, tetrapropylammonium ions, tetraethylammonium ions, tetramethylammonium ions, etc., can preferably be used, but tetrabutylammonium ions (hereinafter referred to as "TBA") can be used. +(also referred to as ").) can be particularly preferably used. Further, as a material for supplying a bulky guest, the above quaternary ammonium salt can be preferably used, and tetrabutylammonium hydroxide can be particularly preferably used.

[0073] For example, consider the case of using Rb4W as a composite tungsten oxide having a layered crystal structure as a raw material. 11 O 35 As shown in Fig. 3(A), Rb4W 11 O 35 has a layered crystal structure in which a layer 31 in which a six-membered ring structure is arranged as a repeating structure of tungsten-oxygen octahedron blocks and a plane 32 in which only Rb exists are alternately laminated. That is, it has a structure in which alkali metal Rb exists between the layers of layer 31. The six-membered ring structure of the octahedron block is a hexagonal tungsten bronze structure, and a one-dimensional tunnel of Rb exists in the six-membered ring structure. When acid treatment is applied to Rb4W 11 O 35 having this layered crystal structure, a part or all of Rb existing on the plane 32 is extracted as ions into the acid aqueous solution, and hydrogen ions or oxonium ions are introduced into the voids to obtain a hydrogen-type substance. At this time, depending on the acid treatment conditions, Rb existing in the one-dimensional tunnel in the six-membered ring structure of layer 31 may also be extracted during the acid treatment. Next, the hydrogen-type substance is added to a liquid containing a quaternary ammonium ion or the like that functions as a bulky guest, and the liquid is mixed and shaken. By performing such an operation, the hydrogen-type substance can be peeled off to a single layer while maintaining the six-membered ring structure of layer 31 and the one-dimensional tunnel of Rb, and a molecular film of layer 31 can be obtained. At this time, since the quaternary ammonium that functions as a bulky guest acts as a surface modifier and a dispersant of the molecular film, the molecular film is obtained in a dispersed state in the liquid, that is, a dispersion liquid containing the molecular film is obtained. The dispersion liquid can be used as a coating liquid, for example, in a coating step when manufacturing a conductor described later.

[0074] Depending on acid treatment conditions such as the type, concentration, and number of treatments of the acid, for example, the general formula Rb 4-a H aW 11 O 35 The amount of a in a hydrogen-type substance represented by (0 ≤ a ≤ 4), i.e., the amount of ion exchange, can be changed. For example, when all of the Rb present on surface 32 undergoes ion exchange, a = 1 and Rb 3HW 11 O 35 A hydrogen-type substance is obtained, Rb3W 11 O 35 - A molecular film of the following is obtained. In addition, when all of the Rb present in the one-dimensional tunnel within the six-membered ring structure of layer 31 is also ion-exchanged, H4W 11 O 35 A hydrogen-type substance is obtained, W 11 O 35 4- A molecular film of the following is obtained. 11 O 35 - and W 11 O 35 4- Both molecular films have negatively charged surfaces. Normally, the maximum charge of W is 6+, so the molecular films have charge states of -1 and -4, respectively. However, as the molecular films are formed, bulky guest ions modify the molecular film surface, so the overall state, including the bulky guest, is thought to be close to neutral.

[0075] Here, from the viewpoint of ensuring that the reaction to exfoliate the hydrogen-type material after acid treatment down to a single layer proceeds sufficiently, it is preferable to perform ion exchange of a=1 or more, which corresponds to the amount of Rb ions present on surface 32, i.e., the amount of Rb ions present between layers of layer 31. Therefore, it is preferable to perform the acid treatment such that a is 1 or more in the above general formula, using hydrochloric acid with a concentration of 6 N or more, or nitric acid, sulfuric acid, or carbonic acid in an (solid) / (aqueous solution) ratio of 1 g / 100 cm -3 It is preferable to perform the acid treatment with the following solid-liquid ratio. However, this is done using Rb4W as the raw material. 11 O 35 These are the preferred acid treatment conditions when using [specific material], and the preferred conditions will vary depending on the raw materials used.

[0076] The amount of bulky guest added is not particularly limited, but for example, Rb 4-a H aW 11 O 35 TBA is a bulky guest ion relative to the amount of hydrogen ions in hydrogen-type substances represented by (0≦a≦4). + It is preferable to add the substance such that its molar ratio is in the range of 0.5 to 2. By setting the molar ratio to 0.5 or higher, interlayer delamination can be particularly sufficiently promoted. Furthermore, by setting the molar ratio to 2 or lower, the collapse of the hydrogen-type substance and the crystalline structure of the molecular film can be prevented. More preferably, the molecular film can be obtained with the best yield when the molar ratio is around 1.

[0077] The size of the resulting molecular film is not particularly limited, but it can have a thickness equivalent to a single layer of layer 31, for example, a thickness of 2 nm to 3 nm. However, the thickness of the molecular film is not limited to this range, and the thickness can be selected depending on the raw materials used.

[0078] Furthermore, the longitudinal length of the resulting molecular film can be, for example, between 20 nm and 1 mm. That is, the aspect ratio can be, for example, between 7 and 500,000. This can be controlled by adjusting the synthesis (calcination) temperature of the composite tungsten oxide having a layered crystalline structure, which is the raw material, or by using single crystals of composite tungsten oxide or tungsten oxide. In addition, the molecular film can be broken down by stirring or ultrasonic irradiation of the dispersion containing the obtained molecular film. For example, by applying gentle stirring, the length can be controlled to a width (longitudinal direction) of 1 μm or more, and by applying a strong shear force such as ultrasonic irradiation, the length can be controlled to a width of less than 1 μm. However, synthesizing a huge molecular film with a length longer than 1 mm is difficult at present.

[0079] Furthermore, any unreacted substances generated in the above reaction can be removed by further centrifugation of the dispersion containing the resulting molecular film.

[0080] The molecular film of this embodiment can also have its conductive properties enhanced by introducing oxygen vacancies through a reduction treatment. The method of reduction treatment is not particularly limited, but examples include a wet method in which an appropriate reducing agent is added at the same time as peeling off the hydrogen-type substance described above, or an appropriate reducing agent is added after obtaining a dispersion containing the molecular film, and a dry method in which heat treatment is performed using a reducing gas. Both the wet and dry methods can also be used in combination. When using a substrate, it is desirable to complete the reduction treatment as a molecular film aggregate after laying down a large number of molecular films on the substrate. Alternatively, the reduction treatment can be completed as a structure by adding an appropriate reducing agent when obtaining the structure described later.

[0081] The preferred conditions for reduction treatment using the dry method will be explained in the heat treatment step of the method for manufacturing conductors, which will be described later. [conductor] The conductor of this embodiment may contain the molecular films described above. Furthermore, the conductor of this embodiment may include molecular film assemblies having multiple molecular films described above. The conductor can be composed of a molecular film assemblies alone, a molecular film alone, or a laminated structure described later, and can exhibit conductive properties even in a locally supported, free-standing state without a substrate. The conductor of this embodiment may also have a film shape; in this case, the conductor of this embodiment can also be called a conductive film.

[0082] Furthermore, the conductor of this embodiment may also include a substrate and a molecular film aggregate disposed on the substrate.

[0083] As an example of a case where the conductor of this embodiment has a substrate, a schematic cross-sectional view of a plane perpendicular to the substrate is shown in Figure 6. As shown in Figure 6, the conductor 60, which is an example of this embodiment, can have, for example, a substrate 61 and a molecular film 62 disposed on at least one surface 61A of the substrate 61.

[0084] Figure 6 shows an example in which a molecular film 62 is provided only on one surface 61A of the substrate 61, but a molecular film can also be provided on the other surface 61B of the substrate 61. The molecular film provided on one surface 61A and the molecular film provided on the other surface 61B may have the same materials and composition, or they may be different. In the conductor 60 shown in Figure 6, an example is shown in which one molecular film 62 is provided on the substrate 61, but the invention is not limited to this form, and for example, multiple molecular films 62 can be provided on the substrate 61 to form a molecular film aggregate.

[0085] Furthermore, the conductor may have a stacked structure in which multiple molecular films 62 are stacked, as shown in Figure 7, but the stacked structure will be described in detail later.

[0086] Furthermore, as shown in Figure 8, the conductor 80 may also have a molecular film 62 and conductive particles 81 other than the molecular film. In the conductor 80, the molecular film 62 and the conductive particles 81 are composited to form a single layer. Note that the conductor 80, which includes a composite layer of the molecular film 62 and conductive particles 81, may also have a substrate 61 as shown in Figure 8, or it may have a configuration without a substrate 61.

[0087] As shown in Figure 9, when the conductor 90 contains conductive particles 81, the conductor 90 may also have a layered structure, which is a molecular film aggregate 92 formed by stacking molecular films 62. The conductor 90 may also have a configuration in which conductive particles 81 are arranged between the molecular films 62 that constitute the molecular film aggregate 92. The conductive particles 81 are not particularly limited, and various conductive materials can be used.

[0088] As will be described later, by heat-treating the molecular film aggregate, the adjacent molecular films 62 react and crystallites can be grown. For example, by heat-treating the conductor 70 shown in Figure 7, it is possible to obtain a molecular film 102 with a single crystallite 101, as shown in the conductor 100 shown in Figure 10. In addition, the conductor 100 may be a polycrystalline molecular film 102 in which only some of the molecular films 62 react and contain multiple crystallites. In this case, the molecular film 102 may also contain voids 103 resulting from the gaps between the molecular films 62 in the conductor 70 shown in Figure 7 before heat treatment.

[0089] In addition, conductors can also have a matrix, as shown in Figures 11 to 15, but the matrix will be described in detail later.

[0090] The following describes the conductors of this embodiment, specifically (1) when the conductor has a substrate, and (2) when the conductor has a laminated structure. (1) When the conductor has a substrate The substrate 61 can be any substrate capable of supporting a molecular film or molecular film aggregate, and its material and shape are not particularly limited. Since conductors are often used in transparent electrodes for displays, it is preferable that the conductor has one of the following shapes: sheet, board, or film. For this reason, it is also preferable that the substrate 61 has one of the following shapes: sheet, board, or film.

[0091] The material of the base material 61 is not particularly limited and can be selected according to the wavelength range of light to be transmitted, absorbed, and reflected as required by the conductor, as well as the required strength, thickness, etc.

[0092] The substrate 61 may include one or more materials selected from single-crystal materials, polycrystalline materials, glass, metals, alloys, ceramics, and resins. The substrate 61 may be composed of any of the above materials, and may be a single-crystal material substrate, a polycrystalline material substrate, a glass substrate, a metal substrate, an alloy substrate, a ceramic substrate, or a resin substrate. In addition, the substrate 61 may have a coating on its surface if necessary.

[0093] When the substrate 61 includes a single crystal material, the single crystal material is not particularly limited, but includes silicon substrates, silicon substrates with oxide films, silver substrates, aluminum substrates, gold substrates, bismuth substrates, cadmium substrates, cobalt substrates, chromium substrates, copper substrates, dysprosium substrates, erbium substrates, iron substrates, germanium substrates, gadolinium substrates, hafnium substrates, holmium substrates, indium substrates, iridium substrates, lithium substrates, magnesium substrates, molybdenum substrates, niobium substrates, nickel substrates, nickel-aluminum substrates, lead substrates, palladium substrates, platinum substrates, rhenium substrates, rhodium substrates, ruthenium substrates, antimony substrates, tin substrates, tantalum substrates, terbium substrates, tellurium substrates, titanium substrates, vanadium substrates, tungsten substrates, yttrium substrates, zinc substrates, zirconium substrates, alloy crystal substrates, silicon carbide substrates, gallium nitride substrates, gallium phosphide substrates, and indium phosphide substrates. One or more substrates selected from the following are available: substrates, lithium fluoride substrates, lanthanum fluoride substrates, magnesium fluoride substrates, strontium fluoride substrates, potassium bromide substrates, potassium chloride substrates, sodium chloride substrates, mica substrates, aluminum oxide substrates, titanium oxide substrates, cobalt oxide substrates, chromium oxide substrates, manganese oxide substrates, nickel oxide substrates, tin oxide substrates, zinc oxide substrates, copper oxide substrates, iron oxide substrates, strontium titanate substrates, lithium niobate substrates, lithium tantalate substrates, potassium tantalate substrates, yttrium aluminate substrates, lanthanum aluminate substrates, lanthanum strontium aluminate substrates, lanthanum gallate strontium gallate substrates, dysprosium scandiate substrates, gadolinium scandiate substrates, neodymium scandiate substrates, gadolinium-gallium-garnet substrates, and yttrium-aluminum-garnet substrates.

[0094] If the base material 61 includes a polycrystalline material, a base material made of the same material as the single-crystal material described above can be suitably used, except that the constituent material is polycrystalline.

[0095] When the base material 61 includes glass, the glass material is not particularly limited, but it is preferably one or more types selected from various functional glasses such as fused silica glass, synthetic silica glass, soda-lime glass, borosilicate glass, crystal glass, alkali-free glass, lead glass, uranium glass, tempered glass, heat-resistant glass, heat-absorbing glass, and Low-E glass.

[0096] If the base material 61 contains a metal, the specific material is not particularly limited, but it is preferably one or more selected from, for example, silver, aluminum, gold, bismuth, cadmium, cobalt, chromium, copper, dysprosium, erbium, iron, gallium, germanium, gadolinium, hafnium, holmium, indium, iridium, lithium, magnesium, molybdenum, niobium, nickel, lead, palladium, platinum, rhenium, rhodium, ruthenium, antimony, scandium, tin, tantalum, terbium, titanium, vanadium, tungsten, yttrium, zinc, zirconium, and SUS (stainless steel).

[0097] If the base material 61 contains an alloy, the material is not particularly limited, but it is preferably one or more selected from, for example, aluminum alloy, gold alloy, cobalt alloy, chromium alloy, copper alloy, iron-based alloy, germanium alloy, magnesium alloy, manganese alloy, nickel alloy, palladium alloy, platinum alloy, titanium alloy, tungsten alloy, and zirconium alloy.

[0098] When the base material 61 includes ceramics, the specific material is not particularly limited, but it is preferable that it be one or more types selected from, for example, oxides, borides, carbides, and nitrides. Note that ceramics overlap with single-crystal materials, polycrystalline materials, and glass.

[0099] When the base material 61 contains a resin, the resin used is not particularly limited, but it is preferable that the resin does not cause any problems with the surface condition or durability of the base material containing the resin. Examples of resins include polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyethylene-2,6-naphthalate; cellulose polymers such as diacetylcellulose and triacetylcellulose; carbonate polymers such as polycarbonate; acrylic polymers such as polymethyl methacrylate; styrene polymers such as polystyrene and acrylonitrile-styrene copolymers; olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; vinyl chloride polymers; amide polymers such as aromatic polyamides; ether polymers such as polyethersulfone and polyetheretherketone; imide polymers; sulfone polymers; phenylene sulfide polymers; vinylidene chloride polymers; oxymethylene polymers; epoxy polymers; vinyl alcohol polymers; polyvinyl acetals such as polyvinyl butyral; and any resin selected from two or more of these resin groups, including various copolymers, graft copolymers, and blends of binary and ternary systems. If the base material 61 contains a resin, it is preferable that the resin is one or more selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polycarbonate, polymethyl methacrylate, and polyvinyl butyral. In particular, it is more preferable in terms of mechanical properties, optical properties, heat resistance, and economics if the base material 61 is a polyester-based biaxially oriented film such as polyethylene terephthalate. The polyester-based biaxially oriented film may also be a copolymerized polyester.

[0100] The thickness of the substrate 61 is not particularly limited and can be selected according to the strength required for the conductor, optical properties, etc. For example, it is preferably 0.001 mm or more and 100 mm or less, and more preferably 0.01 mm or more and 30 mm or less. (2) When the conductor has a laminated structure The conductor may have a layered structure, and from the viewpoint of exhibiting excellent conductive properties, it is preferable to have a layered structure in which multiple molecular films are stacked. In other words, the conductor may include a molecular film aggregate in which molecular films are stacked.

[0101] In other words, in the conductor 60 shown in Figure 6, instead of the region 601 where the molecular film 62 is arranged, the conductor can also have a laminated structure in which the molecular film 62 is arranged in a stacked manner. Specifically, for example, as in the conductor 70 shown in Figure 7, the conductor can have a laminated structure 71 which is a molecular film aggregate 72 in which the molecular film 62 is arranged in a stacked manner on at least one surface 61A of the substrate 61. Figure 7 is a schematic cross-sectional view of the conductor 70 of this embodiment in a plane along the stacking direction. Even when the conductor has a laminated structure, the conductor may have a substrate as shown in Figure 7, or it may not have a substrate, i.e., it may consist only of the laminated structure 71.

[0102] The molecular films 62 constituting the laminated structure 71 may include molecular films 62 with different compositions, etc. Furthermore, as shown in the conductor 90 in Figure 9, the laminated structure 71 may also contain conductive materials such as conductive particles.

[0103] Figure 7 shows an example in which the laminated structure 71, which is a molecular film aggregate 72, is arranged only on one surface 61A of the substrate 61, but the configuration is not limited to this. For example, the laminated structure 71 may also be arranged on the other surface 61B of the substrate 61. Alternatively, a layer containing a molecular film 62 that is not a laminated structure may be arranged on the other surface 61B of the substrate 61. [Method for manufacturing conductive materials] Next, the method for manufacturing the conductor according to this embodiment will be described. Note that the conductor described above can be manufactured using the method for manufacturing the conductor according to this embodiment. Therefore, the matters already explained will be omitted from this description.

[0104] The method for manufacturing the conductive material according to this embodiment may include the following coating step and heat treatment step.

[0105] In the coating process, a dispersion containing a molecular film can be applied to the surface of the substrate.

[0106] In the heat treatment process, the substrate after the coating process can be heat-treated in an atmosphere containing one or more gases selected from inert gases and reducing gases, or in a vacuum.

[0107] According to the method for manufacturing a conductor of this embodiment, a conductor can be manufactured that includes a molecular film containing tungsten element, or a molecular film aggregate containing said molecular film. The molecular film is, as previously described, of the general formula M x W y O z Composite tungsten oxides and general formula W are denoted as such. y O z It may also contain tungsten oxides, as indicated by the formula. Furthermore, the molecular film may have oxygen vacancies, as previously described.

[0108] The following describes each step. (1) Coating process In the coating process, as described above, a dispersion containing a molecular film can be applied to at least one surface of the substrate. This allows for the creation of a molecular film or a molecular film aggregate. Here, the dispersion containing the molecular film is referred to as the coating solution.

[0109] The dispersion containing the molecular film obtained as described above in the method for producing molecular films may be used as a coating solution by adding a surfactant, for example, to ensure particularly uniform application on a substrate during coating. Various types of surfactants can be used, such as nonionic, anionic, cationic, and amphoteric surfactants, depending on the purpose and the material of the substrate.

[0110] The method of applying the coating solution to the substrate surface is not particularly limited, but it is preferable to apply it uniformly so that the substrate surface and the main surface of the molecular film are parallel. For example, the coating solution can be applied to the substrate surface by wet methods such as bar coating, dip coating, electrophoresis, spray coating, spin coating, Langmuir-Blodgett method (LB method), alternating adsorption method (layer-by-layer method), and the single-droplet method described in Non-Patent Literature 1. Because the molecular film of the dispersion has a large aspect ratio, the substrate surface and the main surface of the molecular film tend to be parallel regardless of the coating method, making it easy to apply uniformly. Furthermore, from the viewpoint of applying only a single layer of the molecular film over a wide area while accumulating the molecular film, it is more preferable to employ one or more methods selected from spin coating, Langmuir-Blodgett method, alternating adsorption method, and single-droplet method. Among these methods, the single-droplet accumulation method is particularly preferable because it is simple to use and minimizes the consumption of molecular films.

[0111] Furthermore, after applying the coating solution to the substrate surface, drying or heat treatment at a lower temperature than the heat treatment temperature in the heat treatment process described later can be performed as needed.

[0112] Furthermore, as described above, the conductive material of this embodiment may have a laminated structure, so the coating process may be repeated as needed, or the coating process and the heat treatment such as drying may be repeated alternately. (2) Heat treatment process As described above, in the heat treatment process, after the coating process is completed, the heat treatment can be performed in an atmosphere containing one or more gases selected from inert gases and reducing gases, or in a vacuum. In particular, it is preferable to perform the heat treatment in a reducing gas atmosphere.

[0113] The reducing gas is not particularly limited, but H2 (hydrogen) is preferred. When H2 is used as the reducing gas, the composition of the reducing atmosphere is preferably such that H2 is mixed with an inert gas such as Ar or N2 in a volume ratio of more than 0% to 5.0% or less. The inert gas is also not particularly limited, but from a cost standpoint, one or more selected from the above-mentioned Ar and N2 are preferred.

[0114] The heat treatment temperature is not particularly limited, but for example, 400°C to 700°C is preferred, 500°C to less than 700°C is more preferred, and 550°C to 650°C is even more preferred. By heat treating the molecular film at 400°C or higher, oxygen vacancies can be introduced into the tungsten-oxygen octahedral blocks. Furthermore, the rearrangement of atoms contained in the molecular film can be performed, increasing crystallinity and conductivity. Heat treatment at 400°C or higher can also promote reactions between adjacent molecular films, thereby increasing the crystallite size. Heat treatment at 700°C or lower can suppress the formation of by-products, reactions between the molecular film and the substrate, and sublimation of the molecular film. (3) Separation process The method for manufacturing the conductor in this embodiment may further include any optional steps, such as a separation step for separating the conductor from the substrate. Depending on the material of the substrate, the conductor can be separated from the substrate by, for example, dissolving only the substrate or peeling the conductor off the substrate. The separated conductor can be placed on another substrate or arranged in a structure described later. [Structure] Next, the structure of this embodiment will be described.

[0115] The structure of this embodiment may include the molecular film described above. In addition, in the structure of this embodiment, the molecular film may also take the form of a molecular film aggregate or a conductor as described above. Therefore, the structure of this embodiment may include one or more selected from molecular films, molecular film aggregates, and conductors.

[0116] The structure of this embodiment may also have, for example, a matrix such as a solid medium and the molecular film described above disposed within the matrix. A conductive matrix having electrical conductivity can preferably be used as the matrix. In this case as well, the molecular film within the matrix may have the form of a molecular film aggregate or a conductor as described above. Therefore, the structure of this embodiment may include a matrix and one or more selected from molecular films, molecular film aggregates, and conductors disposed within the matrix.

[0117] As described above, the structure of this embodiment may have a matrix of a suitable solid medium having conductivity, and a molecular film, which is a filler, arranged in the matrix by kneading or other means. The matrix generally refers to the base material, but here it refers to the solid medium into which the molecular film, which is the filler, is kneaded.

[0118] The structure of this embodiment may have a matrix 111 and a molecular film 62 disposed within the matrix 111, for example, as shown in the structure 110 in Figure 11. The molecular film 62 can be disposed within the matrix 111 in the form of individual molecular films as described above. Alternatively, the molecular film 62 may be disposed within the matrix 111 as a molecular film aggregate 72, as illustrated in Figure 12, or it may be disposed within the matrix in the form of a conductor.

[0119] The structure of this embodiment may have a matrix 111 and a molecular film 62 disposed within the matrix 111, for example, as shown in the structure 120 in Figure 12. In the case of the structure 120 shown in Figure 12, the molecular film 62 is shown as a conductor 70 having a substrate 61 and a molecular film aggregate 72 having a laminated structure in which the molecular film 62 is stacked on the substrate 61, and then disposed within the matrix 111. When a conductor containing the molecular film is used when arranging the molecular film within the matrix 111, various conductors described with reference to Figures 6 and 8 to 10 can be used instead of the conductor 70 with the structure shown in Figure 12.

[0120] Thus, the structure of this embodiment can also incorporate a conductor, such as a molecular film aggregate, placed on the substrate, into the matrix together with the substrate. That is, the structure can include a substrate in the matrix, and more specifically, it can include a conductor having a substrate and a molecular film aggregate, etc., placed on the substrate.

[0121] As shown in Figure 13, the structure of this embodiment may also have a base material. That is, the structure 130 may have a base material 131 and a matrix 111 containing the aforementioned molecular film 62 provided on the base material 131.

[0122] For example, as in the case of structure 140 shown in Figure 14, the molecular film placed within the matrix 111 can be in the form of a substrate 61 and a conductor 60 having a molecular film 62 on the substrate 61. Alternatively, instead of the conductor in the structure shown in Figure 14, various conductors described using Figures 7 to 10 can be used as the conductor.

[0123] Furthermore, as shown in Figure 15, the structure of this embodiment may also contain conductive particles 151. The conductive particles 151 can be arranged, for example, within the matrix 111. The conductive particles 151 can be a molecular film, a molecular film aggregate, or a component other than a conductor. The conductive particles 151 are not particularly limited, and various conductive materials can be used. Examples of conductive particles include metal particles such as Ag and Au, and WO 3-x Tungsten oxide particles such as Cs 0.33 WO 3-x Examples include composite tungsten oxide particles such as LaB6, hexaboride particles such as In2O3:Sn, element-doped indium oxide particles such as SnO2:Sb, and element-doped zinc oxide particles such as ZnO:Ga.

[0124] In the structure 150, the conductive particles 151 and the matrix 111 containing the molecular film 62 can also be provided on the substrate 131. The structure 150 may also be provided without the substrate 131.

[0125] Furthermore, since the structures shown in Figures 13 to 15 are formed on a substrate, they could also be classified as conductors rather than structures.

[0126] The matrix can be any matrix into which a molecular film, molecular film aggregate, or conductor can be incorporated, and its shape is not particularly limited. Since the structure of this embodiment is often used in electrodes, electrical circuits, etc., it is preferable that it has one of the following shapes: sheet, board, or film. For this reason, it is also preferable that the matrix has one of the following shapes: sheet, board, or film.

[0127] The matrix material is not particularly limited and can be selected according to the wavelength range of light to be transmitted, absorbed, and reflected by the structure, as well as the required strength, thickness, electrical properties, etc.

[0128] The matrix can contain conductive materials similar to those of the substrate described above, but it is preferable to include a resin from the viewpoint of ease of processing when incorporating molecular films, etc., as well as lightness, cost-effectiveness, and durability. Since resins have a low softening point, it is easy to obtain a matrix in the form of a sheet, board, or film with filler molecular films, etc., incorporated by melt mixing and stretching.

[0129] The resin used is not particularly limited, but it is preferable that it does not cause any problems with the surface condition or durability of the matrix containing the resin. As the resin, for example, it can be suitably selected from the materials described in the section "(1) When the conductor has a base material" of the conductor described above, specifically in the case where the base material 61 contains a resin. In particular, it is more preferable in terms of conductivity, mechanical properties, optical properties, heat resistance and economy that the resin be one or more conductive polymers selected from polyacetylene, polythiophene, poly(p-phenylene vinylene), polypyrrole, polyaniline, and poly(p-phenylene sulfide). [Examples]

[0130] The present invention will be described in detail below with reference to the following examples. However, the present invention is not limited to the following examples. [Example 1] (Preparation of the coating solution) First, the coating solution was prepared according to the following procedure.

[0131] 16.1 g of cesium carbonate and 40.0 g of tungsten(VI) oxide were mixed to achieve a molar ratio of Cs:W of 6.3:11, and the mixture was calcined at 900°C for 5 hours in an air atmosphere. The powder X-ray diffraction pattern of the calcined material revealed Cs6W 11 O 36 We confirmed that the obtained Cs6W was obtained. The composition is shown in the "Composition of the fired product" column of Table 1. 11 O 36 It was also confirmed that the basic framework consists of repeating tungsten-oxygen octahedral blocks. The powder X-ray diffraction pattern was measured using powder X-ray diffraction (θ-2θ method) with an X-ray diffractometer (SmartLab, a fully automated multi-purpose X-ray diffractometer manufactured by Rigaku Corporation).

[0132] The obtained Cs6W 11 O 36 0.5 g was taken and immersed in 50 mL of 6 N hydrochloric acid. Next, the mixture was mixed and shaken for 1 day at a shaking speed of 150 rpm using a shaker (Azwan Corporation Lab Shaker SR-1) at room temperature, i.e., without any heat treatment such as heating or cooling. Furthermore, after removing the hydrochloric acid by decantation, the solution was replaced with fresh hydrochloric acid and the same acid treatment was performed for an additional day. The solid residue of the hydrogen-type substance, which was the acid-treated product, was recovered by filtration, washing with water, and air drying (acid treatment process).

[0133] The Cs and W concentrations of the obtained solid residue were analyzed using an ICP emission spectrometer (Shimadzu Corporation, model ICPE-9000), and were found to be 17 wt% and 64 wt%, respectively. Furthermore, the chemical formula was calculated from these results, confirming that the solid residue had a molar ratio of Cs / W = 4 / 11. In Table 1, under the column for hydrogen-type substances, the columns for each element (Cs, Rb, and W) show the mass percentage of each element in the obtained hydrogen-type substance, while the columns for Cs / W and Rb / W show the molar ratio of Cs or Rb to W, respectively.

[0134] To 0.4 g of the obtained solid residue, add 100 cm³ of a 0.0029 mol / L aqueous solution of tetrabutylammonium hydroxide. 3 Next, the mixture was mixed and shaken in a shaker at a shaking speed of 150 rpm for 14 days, and then the settled components were removed by centrifugation to obtain the stock solution for coating according to Example 1, Cs4W 11 O 36 2- A dispersion containing a molecular film was obtained (colloidalization step). Here, the molecular film is obtained in a negatively charged state, but the surface of the molecular film is TBA of tetrabutylammonium ions. + It is modified, and the overall state is considered to be close to neutral.

[0135] The resulting Cs4W 11 O 36 2- A dispersion containing the molecular film was dropped onto a microgrid for transmission electron microscopy, and the molecular film was transferred and its morphology was observed using a transmission electron microscope. For the 10 molecular films observed, it was confirmed that the average longitudinal length of the molecular film was 5 μm. Furthermore, analysis of the crystal structure from the electron diffraction pattern of the molecular film revealed that the obtained molecular film was Cs6W before acid treatment. 11 O 36 Similarly, we were able to confirm that it is a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework.

[0136] The resulting stock solution for coating is Cs4W 11 O 36 2-A coating solution according to Example 1 was prepared by mixing 0.1 mL of a dispersion containing the molecular film of Cs3W, 5.0 mL of pure water, and 0.03 mL of ethanol. This solution was then used to perform the coating process by single-droplet deposition. After heating the substrate, a quartz substrate, to 120°C on a hot plate, the coating solution according to Example 1 was dropped onto the quartz substrate and slowly drawn up with a pipette. 11 O 35 - A molecular film assembly composed of these materials was fabricated on a quartz substrate.

[0137] The series of coating operations using the single-droplet deposition method were repeated a total of 10 times to stack molecular film assemblies.

[0138] The X-ray diffraction pattern of a molecular film aggregate, which is a coated film of a molecular film formed on a 1 mm thick quartz substrate, was measured using in-plane X-ray diffraction with an X-ray diffractometer. Analysis of the X-ray diffraction pattern confirmed that the molecular film aggregate contains a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework. Furthermore, since all diffraction peaks originated from this molecular film, it was confirmed that the obtained coated film contains this molecular film as the main component of the crystalline material.

[0139] Then, the substrate was heated under a supply of a gas containing 4% by volume of H2 gas, with Ar gas as the carrier gas, and subjected to a reducing heat treatment at 550°C for 30 minutes. As a result, Cs4W was produced on one surface of the substrate. 11 O z A conductive film (conductor) according to Example 1 was obtained, comprising a conductive oxide molecular film aggregate containing a conductive oxide molecular film consisting of (z<36). (Heat treatment step) The X-ray diffraction pattern of the conductive film according to Example 1 was measured using an X-ray diffractometer with in-plane X-ray diffraction. Analysis of the X-ray diffraction pattern confirmed that the conductive film according to Example 1 contains a molecular film aggregate that includes a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework.

[0140] Carbon was deposited onto the conductive film according to Example 1, and a cross-sectional thin section (less than 100 nm thick) was prepared using a focused ion beam (FIB) processing apparatus. The cross-sectional thin section was then observed using a transmission electron microscope (JEOL JEM-ARM200F), and atomic resolution images were obtained. Lattice fringes, which appear to be a repeating structure of tungsten-oxygen octahedral blocks, were confirmed. Atomic resolution images were examined at multiple locations, and crystallites were identified from the lattice fringes. Sheet-like crystallites were confirmed at all locations. The thickness of the sheet-like crystallites was measured at 10 measurement points 50 nm apart from each other, and the average of the measurements at these 10 points was calculated to be 11 nm.

[0141] The conductive film according to Example 1 was analyzed by X-ray photoelectron spectroscopy (XPS: ULVAC-PHI XPS-Versa Probe III). Photoelectrons excited by irradiation with 25W Al-KαX-rays were measured, and the W4f spectrum observed around 30eV~45eV was obtained by peak fitting. 7 / 2 6+ W4f 5 / 2 6+ W4f 7 / 2 5+ W4f 5 / 2 5+ W5p 3 / 2 The peaks were separated into five. The ratio of W valencies 6+ and 5+ was determined from the intensity area of ​​each peak. 6+ 92.12%, W 5+ The result was 7.88%. Calculating the composition from this, we get Cs4W 11 O z The value of z was 35.6. That is, the composition of the conductive oxide molecular film constituting the conductive oxide molecular film aggregate in the conductive film according to Example 1 is Cs4W 11 O 35.6 We were able to confirm that this was the case.

[0142] Here, we will explain how to calculate z. Cs4W 11 O z The charge state is not certain, but assuming that z takes its maximum value, Cs4W is the same as before heat treatment. 11 Oz Assume that the element is negatively charged with a charge of -2. Since the valence of Cs is +1, considering the charge balance, we get 4×1 + 11×(92.12×6 + 7.88×5) / 100 - 2×z = -2. Solving this, we get z = 35.6. The same calculation method was used in subsequent examples.

[0143] The transparency of the obtained conductive film was evaluated using a spectrophotometer (UH4150, Hitachi High-Tech Science Co., Ltd.). Transmitted light profiles were measured at 5 nm intervals in the wavelength range of 200 nm to 800 nm, and the visible light transmittance was calculated in the wavelength range of 380 nm to 780 nm based on JIS R 3106 (2019), resulting in a visible light transmittance of 81%.

[0144] The mobility and carrier density of the obtained conductive film were evaluated using a Hall effect measurement controller (Lake Shore M91 FastHall), and the mobility was 120 cm². 2 / (V / s), carrier density is 2.2 × 10⁻⁶ 20 / cm 3 The conductive film obtained in this example had a mobility of 0.01 (cm²). 2 Carrier density of 1.0 × 10⁻¹⁰ or greater (V / s) 19 / cm 3 In conclusion, we were able to confirm that it possesses excellent conductivity. [Example 2] (Preparation of the coating solution) To achieve a molar ratio of Cs:W of 4:11, 10.2 g of cesium carbonate and 40.0 g of tungsten(VI) oxide were mixed and calcined at 850°C for 5 hours in an air atmosphere. The powder X-ray diffraction pattern of the calcined material revealed Cs4W 11 O 35 We confirmed that the obtained Cs4W was obtained. 11 O 35 It was also confirmed that the basic framework is a repeating structure of tungsten-oxygen octahedron blocks.

[0145] The resulting Cs4W 11 O 350.5 g was taken and added to 50 mL of 12 N hydrochloric acid. Acid treatment was carried out at room temperature for 1 day, i.e., without heat treatment such as heating or cooling, by mixing and stirring. Furthermore, after removing the hydrochloric acid by decantation, the solution was replaced with fresh hydrochloric acid and the same acid treatment was carried out for an additional 4 days (total of 5 days of acid treatment). The solid residue, which was the acid-treated product, was recovered by filtration, washing with water, and air drying (acid treatment process).

[0146] The Cs and W concentrations of the obtained solid residue were analyzed using an ICP emission spectrometer (Shimadzu Corporation, model ICPE-9000), and were found to be 13 wt% and 66 wt%, respectively. Furthermore, the chemical formula was calculated from these results, confirming that the solid residue had a molar ratio of Cs / W = 3 / 11.

[0147] To 0.4 g of the obtained solid residue, add 100 cm³ of a 0.0016 mol / L aqueous solution of tetrabutylammonium hydroxide. 3 After adding the following, the mixture was stirred at 200 rpm for 14 days, and then the settled components were removed by centrifugation to obtain the stock solution for coating according to Example 2, Cs3W 11 O 35 - A dispersion containing a molecular film was obtained (colloidalization step). Here, the molecular film is obtained in a negatively charged state, but the surface of the molecular film is TBA of tetrabutylammonium ions. + It is modified, and the overall state is considered to be close to neutral.

[0148] The resulting Cs3W 11 O 35 - A dispersion containing the molecular film was dropped onto a microgrid for transmission electron microscopy, and the molecular film was transferred and its morphology was observed using a transmission electron microscope. For the 10 molecular films observed, it was confirmed that the average longitudinal length of the molecular film was 5 μm. Furthermore, analysis of the crystal structure from the electron diffraction pattern of the molecular film revealed that the obtained molecular film was Cs4W before acid treatment. 11 O 35 Similarly, we were able to confirm that it is a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework.

[0149] Except for using the undiluted coating solution according to Example 2 instead of the undiluted coating solution according to Example 1, the process was carried out in the same manner as in Example 1, and Cs3W 11 O z A conductive film according to Example 2 was obtained, which had a molecular film aggregate containing a molecular film consisting of (z<35). Upon completion of the intermediate coating process, it was confirmed that the molecular film aggregate, which was a coated film of molecular films formed on a 1 mm thick quartz substrate, contained a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework as the main component of the crystalline material.

[0150] By evaluating in the same manner as in Example 1, it was confirmed that the conductive film according to Example 2 also contains a molecular film aggregate that includes a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework. Furthermore, when the thickness of the sheet-like crystallites was observed using a transmission electron microscope and the average of 10 locations was calculated in the same manner as in Example 1, the average value of the crystallite thickness was 12 nm. Analysis by X-ray photoelectron spectroscopy revealed that W 6+ 87.67%, W 5+ The result was 12.33%, and the composition of the molecular film constituting the molecular film aggregate in the conductive film according to Example 2 was Cs3W 11 O 34.3 This was confirmed. Furthermore, in calculating the oxygen content z, Cs3W was used, the same as before heat treatment. 11 O z We assumed that it was negatively charged with a charge of -1.

[0151] When evaluated in the same manner as in Example 1, the visible light transmittance of the conductive film according to Example 2 was 78%, and the mobility was 5.5 cm. 2 / (V / s), carrier density is 1.8 × 10⁻⁶ 22 / cm 3 The conductive film obtained in this example had a mobility of 0.01 (cm²). 2 Carrier density of 1.0 × 10⁻¹⁰ or greater (V / s) 19 / cm 3 In conclusion, we were able to confirm that it possesses excellent conductivity. [Example 3] Except for using the coating solution from Example 2 instead of the coating solution from Example 1, and performing a reduction heat treatment at 500°C for 10 minutes instead of 550°C for 30 minutes, the process was the same as in Example 1, but with respect to Cs3W 11 O z A conductive film according to Example 3 was obtained, which has a molecular film aggregate containing a molecular film consisting of (z<35).

[0152] By evaluating the obtained conductive film in the same manner as in Example 1, it was confirmed that it contained a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework. Furthermore, when the thickness of the sheet-like crystallites was observed using a transmission electron microscope and the average of 10 locations was calculated in the same manner as in Example 1, the average crystallite thickness was 2.5 nm. Analysis by X-ray photoelectron spectroscopy revealed that W 6+ 94.01%, W 5+ The result is 5.99%, and the composition of the molecular film constituting the molecular film aggregate in the conductive film according to Example 3 is Cs3W 11 O 34.7 This was confirmed. Furthermore, in calculating the oxygen content z, Cs3W was used, the same as before heat treatment. 11 O z We assumed that it was negatively charged with a charge of -1.

[0153] When evaluated in the same manner as in Example 1, the visible light transmittance of the conductive film according to Example 3 was 79%, and the mobility was 2.1 cm. 2 / (V / s), carrier density is 1.0 × 10⁻⁶ 22 / cm 3 The conductive film obtained in this example had a mobility of 0.01 (cm²). 2 Carrier density of 1.0 × 10⁻¹⁰ or greater (V / s) 19 / cm 3 In conclusion, we were able to confirm that it possesses excellent conductivity. [Example 4] The series of coating operations in the coating process according to Example 2 were repeated 40 times, and Cs3W 11 O 35 A precursor of a conductive film composed solely of [the specified material] was fabricated on a quartz substrate.

[0154] Then, after undergoing a heat treatment process under the same conditions as in Example 1, Cs3W is applied to one surface of the substrate. 11 O z A conductive film according to Example 3 was obtained, which has a molecular film aggregate containing a molecular film consisting of (z<35).

[0155] By evaluating the molecular film aggregate containing the obtained molecular film in the same manner as in Example 1, it was confirmed that it contained a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework. Furthermore, when observed with a transmission electron microscope and the average thickness of 10 sheet-like crystallites was calculated in the same manner as in Example 1, the average crystallite thickness was 25 nm. Analysis by X-ray photoelectron spectroscopy revealed that W 6+ 87.37%, W 5+ The result was 12.63%, and the composition of the molecular film constituting the molecular film aggregate in the conductive film according to Example 1 was Cs3W 11 O 34.3 This was confirmed. Furthermore, in calculating the oxygen content z, Cs3W was used, the same as before heat treatment. 11 O z We assumed that it was negatively charged with a charge of -1.

[0156] When evaluated in the same manner as in Example 1, the visible light transmittance of the conductive film according to Example 3 was 55%, and the mobility was 13 cm. 2 / (V / s), carrier density is 2.2 × 10⁻⁶ 22 / cm 3 The conductive film obtained in this example had a mobility of 0.01 (cm²). 2 Carrier density of 1.0 × 10⁻¹⁰ or greater (V / s) 19 / cm 3 In conclusion, we were able to confirm that it possesses excellent conductivity. [Example 5] Instead of 10.2 g of cesium carbonate, 7.24 g of rubidium carbonate was used, and in the acid treatment process, the acid treatment was performed for 10 days instead of 5 days. In addition, in the colloidalization process, 100 cm³ of a 0.0016 mol / L aqueous solution of tetrabutylammonium hydroxide was used. 3 Instead, use 100 cm³ of a 0.0014 mol / L aqueous solution of tetrabutylammonium hydroxide. 3The following was used. Except for the points mentioned above, the procedure was the same as in Example 2, and the fired product was Rb4W with a repeating tungsten-oxygen octahedral block structure as the basic framework. 11 O 35 Synthesize Rb3W as the stock solution for the coating solution according to Example 5. 11 O 35 - A dispersion containing a molecular film of Rb3W was obtained. Furthermore, the same procedure as in Example 2 was used, except that the stock solution for coating according to Example 5 was used instead of the stock solution for coating according to Example 2. 11 O z A conductive film according to Example 5 was fabricated, which had a molecular film aggregate containing a molecular film consisting of (z<35).

[0157] Upon collecting the solid residue, which was the acid-treated material during the process, the Rb and W concentrations were analyzed and found to be 9 wt% and 70 wt%, respectively. Furthermore, the chemical formula was calculated from these results, confirming that the solid residue had a molar ratio of Rb / W = 3 / 11.

[0158] By evaluating in the same manner as in Example 1, it was confirmed that the conductive film according to Example 5 also contains a molecular film aggregate that includes a molecular film with a repeating tungsten-oxygen octahedral block structure as its basic framework. Furthermore, when observed with a transmission electron microscope and the average thickness of the sheet-like crystallites was calculated at 10 locations, as in Example 1, the average crystallite thickness was 11 nm. Additionally, analysis by X-ray photoelectron spectroscopy revealed that W 6+ 88.57%, W 5+ The result was 11.43%, and the composition of the molecular film constituting the molecular film aggregate in the conductive film according to Example 5 was Rb3W 11 O 34.4 This was confirmed. Furthermore, in calculating the oxygen content z, Rb3W was used, the same as before heat treatment. 11 O z We assumed that it was negatively charged with a charge of -1.

[0159] When evaluated in the same manner as in Example 1, the visible light transmittance of the conductive film according to Example 4 was 80%, and the mobility was 4.2 cm². 2 / (V / s), carrier density is 3.4 × 10⁻⁶ 21 / cm3 The conductive film obtained in this example had a mobility of 0.01 (cm²). 2 Carrier density of 1.0 × 10⁻¹⁰ or greater (V / s) 19 / cm 3 In conclusion, we were able to confirm that it possesses excellent conductivity. [Example 6] 5.01 g of bismuth(III) oxide and 4.99 g of tungsten(VI) oxide were mixed and heat-treated at 700°C for 5 hours in an air atmosphere. The acquisition of Bi2W2O9 was confirmed from the powder X-ray diffraction pattern of the calcined product.

[0160] 0.5 g of the obtained Bi2W2O9 was taken and added to 50 mL of 6 N hydrochloric acid. Acid treatment was carried out at room temperature for 3 days by mixing and stirring, i.e., without heat treatment such as heating or cooling. Furthermore, after removing the hydrochloric acid by filtration, the solution was replaced with fresh hydrochloric acid and the same acid treatment was carried out for an additional 4 days. Decantation, washing with water, and air drying were performed to recover the solid residue, which was the acid-treated product (acid treatment process).

[0161] Analysis of the obtained solid residue revealed a W concentration of 75 wt%. Bi was not detected.

[0162] To 0.4 g of the obtained solid residue, add 100 cm³ of a 0.017 mol / L aqueous solution of tetrabutylammonium hydroxide. 3 Except for the addition of the following, the process was the same as in Example 1, and the raw material for the coating solution according to Example 6 was W2O7 2- A dispersion containing a molecular film of was obtained (colloidalization step). Then, in the same manner as in Example 1, except that the stock solution for the coating solution according to Example 6 was used instead of the stock solution for the coating solution according to Example 1, W2O z A conductive film according to Example 6 was fabricated, which had a molecular film aggregate containing a molecular film consisting of (z<7).

[0163] By evaluating in the same manner as in Example 1, it was also confirmed that the conductive film according to Example 6 contains a molecular film aggregate including a molecular film having a repeating structure of tungsten-oxygen octahedron blocks as a basic skeleton. Further, when observed by a transmission electron microscope and the average of 10 locations was determined for the thickness of sheet-like crystallites in the same manner as in Example 1, the average value of the crystallite thickness was 10 nm. Also, when analyzed by X-ray photoelectron spectroscopy, W 6+ was 88.80% and W 5+ was 11.20%. It was confirmed that the composition of the molecular film constituting the molecular film aggregate in the conductive film according to Example 6 was W2O 6.89 . In the calculation of the composition, it was assumed that W2O z was negatively charged with a charge state of -2, as before the heat treatment.

[0164] When evaluated in the same manner as in Example 1, the visible light transmittance of the conductive film according to Example 6 was 72%, the mobility was 1.7 (cm 2 / (V / s)), and the carrier density was 1.3×10 22 / cm 3 . The conductive film obtained in this example had a mobility of 0.01 (cm 2 / (V / s)) or more and a carrier density of 1.0×10 19 / cm 3 or more, and it was confirmed that it had excellent conductivity.

[0165]

Table 1

Explanation of Symbols

[0166] 11 Tungsten-oxygen octahedron block 12 Void 13 M 31 Layer<{ 32 Plane 60, 70, 80, 90, 100 Conductor 61 Substrate 61A One side 61B The other side 62, 102 Molecular film 71 Laminated structure 72, 92 Molecular film assembly 81 Conductive particles 101 Crystallite 110, 120, 130, 140, 150 Structure 111 Matrix 131 Substrate

Claims

1. comprising a tungsten-oxygen octahedron block, A conductive oxide molecular film having a mobility of 0.01 cm² / (V·s) or more and 1000 cm² / (V·s) or less.

2. General formula M ｘ W ｙ O ｚ (However, M is H, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Pm , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn, Element group including Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, As, Sb, Bi, S, Se, Te, F, Cl, Br, I, and Bi ２ O ２ OH, H ２ O, H ３ O, NH ４ A conductive oxide molecular film according to claim 1, comprising one or more types selected from a group of atomic groups including, where W is tungsten, O is oxygen, 0.001 ≤ x / y ≤ 1, and 2.0 ≤ z / y ≤ 3.5, comprising a composite tungsten oxide.

3. The conductive oxide molecular film according to claim 2, wherein M comprises one or more selected from H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Fe, Cu, Ag, In, Tl, Sn, Pb, and Yb.

4. The conductive oxide molecular film according to claim 2, wherein M comprises one or more selected from Cs and Rb.

5. General formula W ｙ O ｚ The conductive oxide molecular film according to claim 1, which contains a tungsten oxide represented by (where W is tungsten, O is oxygen, and 2.0 ≦ z / y < 3.5).

6. A conductive oxide molecular film according to claim 1 or claim 2, having chromic properties.

7. Carrier density is 1.0 × 10 １９ / cm ３ The above 1.0 x 10 ２４ / cm ３ The conductive oxide molecular film according to claim 1 or claim 2, wherein the following applies:

8. A conductive oxide molecular film according to claim 1 or claim 2, wherein the average thickness of the crystallites it contains is 2 nm or more.

9. A conductive oxide molecular film aggregate containing the conductive oxide molecular film according to claim 1 or claim 2.

10. A conductor comprising the conductive oxide molecular film aggregate described in claim 9.

11. Substrate and A conductor comprising a conductive oxide molecular film aggregate according to claim 9 disposed on the substrate.

12. The conductor according to claim 10, which includes a laminated structure.

13. A structure comprising a conductive oxide molecular film according to claim 1 or claim 2.

14. The Matrix and The structure according to claim 13, comprising the conductive oxide molecular film disposed in the matrix.

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