Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

• Dispersion for forming transparent conductive film Dispersion for forming transparent conductive film, method for forming transparent conductive film, and transparent electrode
• the present invention relates to a dispersion for forming a transparent conductive film, a method for forming a transparent conductive film, and a transparent electrode, and particularly relates to a field such as an electric and electronic industry including metal fine particles or alloy fine particles and oxide fine particles.
• the present invention relates to a dispersion for forming a transparent conductive film that can be used in the above, a method for forming a transparent conductive film using the dispersion, and a transparent electrode made of the transparent conductive film.
• a transparent electrode made of an oxide such as ITO or ATO is used for an electrode of a flat panel display represented by a liquid crystal display.
• the manufacturing method in this case includes an evaporation method, an ion plating method, a sputtering method, and the like, and a transparent electrode is formed by depositing a metal oxide film on a glass substrate by these methods.
• an ITO film, which is an oxide film is formed by a sputtering method.
• a dispersion of tin-doped indium oxide powder is prepared, the dispersion is applied on a substrate, and after drying, A method of obtaining a transparent conductive film by firing is known (for example, see Patent Document 1).
• Patent Document 1 An oxide film is formed directly on a transparent substrate such as a glass substrate, and the obtained transparent conductive film is used for a flat panel display represented by a liquid crystal or a plasma display.
• the display manufacturing on acrylic substrates which are becoming mainstream along with the increase in size, there is a problem that the substrate is damaged by the film forming technology at such a high temperature of 400 ° C due to the thermal restrictions on the substrates. There is.
• metal ultrafine particles such as Ag ultrafine particles are used to form transparent plastic films and the like. It is also known to form a transparent conductive film on a substrate at a relatively low temperature to obtain a low-resistance film.
• Patent Document 3 See, for example, Patent Document 3. As shown in Patent Document 3, it is possible to reduce the resistance by using Ag, but the ultrafine particles of Ag are colored by plasmon absorption, and if sufficient transmittance cannot be obtained, it is difficult. There is a problem.
• a transparent conductive metal film and a metal oxide film for forming a transparent conductive film are alternately laminated on a substrate in a plurality of layers in this order, and the laminated film is fired for each layer or collectively.
• Low-resistance transparent conductive films are also known (for example, see Patent Document 4). In this case, there is a problem that the manufacturing process becomes complicated.
• an antistatic film there is a technique in which transparent oxide particles having low resistance are used, and conductivity is ensured by contacting the particles.
• a transparent conductive film is formed on the substrate, and then a second layer of film is applied thereon, and the adhesion between the particles is improved by utilizing the heat shrinkage.
• the method of increasing the contact resistance to lower the contact resistance and consequently the surface resistance is reduced. Also in this case, there is a problem that the manufacturing process becomes complicated.
• Patent Document 1 JP-A-07-242842 (Claims, Examples)
• Patent Document 2 Japanese Patent Application Laid-Open No. 2003-249131 (Claims)
• Patent Document 3 Japanese Patent Application Laid-Open No. 2001-176339 (Claims)
• Patent Document 4 Japanese Patent Application Laid-Open No. 2003-249126 (Claims)
• the transmittance is high but the resistance is high when only the oxide fine particles are used, and the resistance is low when only the metal fine particles are used. Phenomenon. Furthermore, when oxide fine particles and metal fine particles are used, there is a problem that the manufacturing process becomes complicated.
• An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a dispersion containing metal fine particles, alloy fine particles or a mixture thereof and a metal-doped oxide,
• An object of the present invention is to provide a method for forming a transparent conductive film having low resistance and high transmittance by low-temperature sintering and a transparent electrode comprising the transparent conductive film.
• the dispersion for forming a transparent conductive film of the present invention comprises fine particles of at least one metal selected from indium, tin, antimony, aluminum and zinc, and two or more metals selected from the metals. At least one kind of alloy fine particles, or a mixture of the metal fine particles and alloy fine particles, with Sn-doped In O, Sb-doped Sn ⁇ , Zn-doped In O, and A1-doped Zn ⁇
• At least one kind of oxide fine particles is mixed and dispersed in an organic solvent.
• a transparent conductive film having low resistance and high transmittance can be formed by low-temperature baking.
• the method for forming a transparent conductive film of the present invention is characterized in that the dispersion for forming a transparent conductive film is applied to a substrate and then fired.
• the calcination is performed in an atmosphere selected from a vacuum atmosphere, an inert gas atmosphere, a reducing gas atmosphere, and an oxidizing gas atmosphere.
• the calcination is performed in an atmosphere in which a metal or alloy selected from a vacuum atmosphere, an inert gas atmosphere, and a reducing gas atmosphere is not oxidized, and then in an oxidizing gas atmosphere.
• firing is further performed in an atmosphere selected from a vacuum atmosphere, an inert atmosphere, and a reducing gas atmosphere.
• a transparent conductive film having low resistance and high transmittance can be formed by low-temperature firing.
• the inert gas atmosphere is an atmosphere composed of at least one inert gas selected from a rare gas, carbon dioxide, and nitrogen, and the reducing gas atmosphere is hydrogen, carbon monoxide, and a lower alcohol.
• the oxidizing gas atmosphere is an atmosphere comprising at least one oxidizing gas selected from oxygen-containing gases.
• the vacuum atmosphere includes at least one inert gas selected from a rare gas, carbon dioxide, and nitrogen, at least one oxidizing gas selected from an oxygen element-containing gas, hydrogen, carbon monoxide, At least one reducing gas selected from lower alcohols, or a mixed gas comprising the inert gas and an oxidizing gas or a reducing gas. To do.
• the oxidizing gas atmosphere contains oxygen, an oxygen-containing gas, water vapor or a water vapor-containing gas.
• the metal fine particles and the alloy fine particles are characterized in that organic compounds are attached around the fine particles. By using such fine particles, the dispersibility of each fine particle is improved, and a uniform conductive film can be obtained.
• the transparent electrode of the present invention is characterized in that the transparent electrode is formed by the transparent conductive film forming method.
• a transparent conductive film is prepared by using a dispersion liquid for forming a transparent conductive film containing specific metal fine particles, alloy fine particles, or a mixture thereof, and specific metal-doped oxide fine particles, at a low temperature.
• the film can be formed by firing, and the obtained film has an effect of having a low resistance and a high transmittance, and can provide a transparent electrode or the like made of this conductive film and which can be used for various applications.
• these fine particles include alloy fine particles unless otherwise specified.
• fine particles of at least one metal of each of the component metals (indium, tin, antimony, aluminum, and zinc) of the metal oxide for forming the transparent conductive film and a metal component of the component Dispersions containing fine particles of at least one alloy composed of at least one kind of metal, mixed fine particles of these metal fine particles and alloy fine particles, and an oxide doped with tin, antimony, aluminum or zinc are: It is a useful dispersion for forming a transparent conductive film.
• the metal oxide used in the present invention includes, for example, IT ⁇ (In-Sn- ⁇ ) (
• Sn range is usually 0 ⁇ 311 ⁇ 20 ⁇ %, preferably 3 ⁇ Sn ⁇ 10wt%), Sb-doped SnO
• A1 doped Zn ⁇ as ⁇ ( ⁇ _ ⁇ 1-0) range of A1 Is usually 0 ⁇ Al ⁇ 20wt%, preferably 5 ⁇ Al ⁇ 15wt%).
• ITO, ⁇ , ⁇ , ⁇ are useful for forming a target transparent conductive film.
• the substrate that can be used in the method for forming a transparent conductive film of the present invention is not particularly limited as long as it is a transparent substrate.
• a low-temperature baking such as an acrylic substrate, a polyimide substrate, or a polyethylene terephthalate (PET) film can be used.
• PET polyethylene terephthalate
• a glass electrode with an organic film such as an organic filter.
• the organic resin material in addition to the above, for example, cellulose acetates, polystyrene, polystyrenes, polyethers, polyimide, epoxy resin, phenoxy resin, polycarbonate, polyvinylidene fluoride, Teflon (registered trademark), etc. It can also be used.
• the shape of the substrate is not particularly limited, and may be, for example, a flat plate, a three-dimensional object, a film, or the like. Note that it is preferable that the substrate to be processed be cleaned using pure water, ultrasonic waves, or the like before applying the dispersion liquid.
• the method of coating the substrate is not particularly limited, and examples thereof include a spin coating method, a spray method, an ink jet method, an immersion method, a roll coating method, a screen printing method, a non-contour printing method and the like. Can be used.
• the coating may be performed once or repeatedly, as long as a desired film thickness can be obtained.
• the dispersion liquid is applied on a substrate to be treated by a known application method, and then a vacuum atmosphere, an inert gas atmosphere, a reducing gas atmosphere, and an oxidizing atmosphere are used.
• the baking treatment is performed in at least two stages in at least two kinds of atmospheres selected from a neutral gas atmosphere.
• firing is first performed in an oxidizing gas atmosphere, the surface resistance of the obtained film increases, which is not preferable.
• firing is performed in an oxidizing gas atmosphere to oxidize the metal fine particles.
• the base material to which the dispersion is applied may be dried at a predetermined temperature to remove the dispersion medium and the like. This removal of the dispersion medium may be performed by a firing process.
• the sintering temperature in the above-described sintering process is controlled by setting the fine metal particles or fine alloy particles It is preferable that the heat-resistant allowable temperature be in a range from the melting point of the core to a temperature lower than the softening point of the substrate to be treated.
• the firing temperature is more preferably, for example, 300 ° C. or lower. Within this temperature range, the substrate will not be damaged.
• a dense film is formed at a lower temperature than in the conventional case, a transparent conductive film having a small electric resistance can be manufactured at a low temperature, and an oxidizing gas atmosphere can be produced.
• the permeability of the obtained membrane can be improved.
• irradiation with a UV lamp during sintering is more effective in reducing time and lowering the temperature.
• a method using a known atmospheric pressure plasma is also effective.
• the vacuum state when the coating film is baked in a vacuum atmosphere, the vacuum state may be determined by simply pulling with a pump or after drawing with an inert gas, a reducing gas, or an oxidizing gas. A neutral gas may be introduced. Firing in a vacuum atmosphere can usually line Ukoto at 10- 5 10 3 Pa about.
• the inert gas atmosphere is, for example, an atmosphere composed of at least one inert gas selected from a rare gas, carbon dioxide, and nitrogen.
• the reducing gas atmosphere is an atmosphere composed of at least one reducing gas selected from hydrogen, carbon monoxide and lower alcohol
• the oxidizing gas atmosphere is
• an atmosphere containing at least one oxidizing gas selected from oxygen element-containing gas for example, oxygen, oxygen-containing gas, water vapor, and water vapor-containing gas. Etc. are included.
• the vacuum atmosphere may contain an inert gas, an oxidizing gas, a reducing gas, or a mixed gas of an inert gas and an oxidizing gas or a reducing gas.
• the lower alcohol in the reducing gas atmosphere is a lower alcohol having 16 to 16 carbon atoms, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol and the like.
• This reducing gas atmosphere is a firing atmosphere for removing only oxygen from the surface of the metal fine particles, and is not an atmosphere for reducing so-called oxides to metal.
• the particle size of the metal fine particles and alloy fine particles used in the present invention is 0.5 nm to 50 nm. Is preferred. When the thickness is less than 0.5 nm, the substantial surface area of the particles increases, and as a result, the amount of organic substances attached around the particles increases. . If it exceeds 50 nm, sedimentation is likely to occur when dispersed in an organic solvent.
• the primary particle diameter of the metal oxide fine particles is preferably about 20 to 30 nm.
• the method for producing the metal fine particles and alloy fine particles used in the present invention is not particularly limited.
• the wet reduction method or the heat treatment by spraying the organometallic compound to a high-temperature atmosphere is used.
• a reduction method or the like may be used.
• the surfaces of the obtained metal fine particles and alloy fine particles are preferably in a metal state, but may be in a state where at least a part thereof is oxidized.
• a metal is evaporated in a gas atmosphere and in a gas phase in which a vapor of a solvent coexists, and the evaporated metal is condensed into uniform fine particles and separated into a solvent. And a dispersion is obtained (for example, Japanese Patent No. 2561537).
• metal fine particles having a uniform particle size of 50 nm or less can be produced.
• the organic solvent may be appropriately selected depending on the type of metal fine particles to be used, and examples thereof include the following. That is, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, hexanol, heptanol, octanol, decanol, cyclohexanol and terpineol, glycols such as ethylene glycol and propylene glycol, acetone , Methylethyl ketone, and ketones such as getyl ketone; esters such as ethyl acetate, butyl acetate, and benzyl acetate; ether alcohols such as methoxyethanol and ethoxyethanol; ethers such as dioxane and tetrahydrofuran.
• alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, hexanol, heptanol,
• Acid amides such as, ⁇ -dimethylformamide; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene and dodecylbenzene; hexane, heptane, octane, Down, decane, Undekan, Liquid at room temperature, such as long-chain alkanes such as dodecane, tridecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane, eicosane, and trimethylpentane; cycloalkanes; What is necessary is just to select and use them appropriately. It is assumed that water is also contained in this organic solvent.
• a solvent such as the above can be used.
• a nonpolar solvent such as toluene, xylene, benzene, or tetradecane; acetone; Ketones such as ethyl ketone, alcohols such as methanol, ethanol, propanol, and butanol can be used.
• the ink When preparing an ink solution for ink-jet printing, the ink must be compatible with the head material (including the surface coating material) (for example, it must have the property of not corroding, dissolving, etc.), and the aggregation of metal fine particles in the head. It is necessary to select an appropriate solvent in consideration of particle clogging.
• the organic solvent may be used alone or in the form of a mixed solvent.
• it may be a mineral spirit that is a mixture of long-chain alkane.
• the amount of the solvent to be used may be appropriately set according to the type and use of the metal fine particles to be used so that the solvent can be easily applied and a desired film thickness can be obtained.
• the concentration of the metal fine particles can be adjusted as needed by heating in a vacuum or the like even after the dispersion liquid is manufactured so that the concentration of the metal fine particles is about 70% by weight.
• the fine metal particles and fine alloy particles used in the present invention may be fine particles having an organic compound attached around the fine particles.
• the metal fine particle dispersion prepared by the gas evaporation method is an organic metal fine particle having a particle diameter of 50 nm or less in an isolated state using at least one selected from alkynoleamine, carboxylic acid amide, and amino carboxylate as a dispersant. It is dispersed in a solvent.
• These metal fine particles are particles having an organic compound as a dispersant adhered to the periphery thereof, and the use of these fine particles facilitates dispersion.
• the alkylamine of the above dispersant may be a primary or tertiary amine, or may be a monoamine, a diamine, or a triamine.
• Alkylamines having main chain carbon atoms of 412 to 20 are preferable, and alkylamines having main chain carbon atoms of 8 to 18 are more preferable in terms of stability and handling. If the carbon number of the main chain of the alkylamine is shorter, the basicity of the amine It is too strong and tends to corrode the metal fine particles, and eventually there is a problem that the metal fine particles are dissolved.
• alkylamines include, for example, butylamine, octylamine, dodecinoleamine, hexadodecylamine, octadecylamine, cocoamine, taroamine, hydrogenated talamine, oleylamine, laurylamine, and stearylamine.
• Secondary amines such as primary amines, dicocoamine, dihydrogenated tallowamine, and distearylamine, and dodecyldimethylamine, didodecylmonomethylamine, tetradecyldimethinoleamine, octadecyldimethyl.
• Tertiary amines such as dimethylamine, cocodimethylamine, dodecyltetradecyldimethinoleamine, and trioctylamine; and, in addition, naphthalenediamine, stearylpropylenediamine, otatamethylenediamine, and Nonandiamine There is a Jiamin like.
• carboxylic acid amide diaminocarboxylate examples include, for example, stearic acid amide, normitic acid amide, lauric acid lauric amide, oleic acid amide, oleic acid diethanolanolamide, oleic acid laurylamide, stearanilide, Oleylaminoethyldaricin and the like.
• the metal fine particles used in the present invention may be a dispersion obtained by a chemical reduction method such as a wet reduction (liquid phase reduction) method.
• a reducing raw material that is a metal-containing organic compound may be used.
• the chemical reduction method is a method for preparing a metal fine particle dispersion by a chemical reaction using a reducing agent.
• the particle diameter can be arbitrarily adjusted to 50 nm or less.
• This reduction method is performed, for example, as follows. In a state where the dispersant is added to the raw material, metal fine particles are generated by using a power or a reducing agent such as hydrogen or sodium borohydride which thermally decomposes the raw material at a predetermined temperature. Almost all the generated metal fine particles are recovered in an independent dispersion state. The particle size of these metal particles is about 50 nm or less. Below. By substituting the metal fine particle dispersion with the organic solvent as described above, a desired metal fine particle dispersion can be obtained. The obtained dispersion maintains a stable dispersion state even when concentrated by heating in vacuum.
• the transparent conductive film formed by the method for forming a transparent conductive film of the present invention as described above includes, for example, a transparent electrode for a flat display, a transparent antistatic film, a transparent electromagnetic wave shielding film, a surface heating element, a transparent electrode antenna, It can be used for solar cells, electronic paper electrodes, transparent electrode gas sensors, etc.
• the In-Sn alloy fine particles in the generation process are produced.
• a 20: 1 (volume ratio) vapor of terpineol and dodecylamine it is cooled and collected to collect the In-Sn alloy fine particles, which are dispersed independently in a-terbineol solvent.
• a dispersion liquid containing 20% by weight of In-Sn alloy fine particles having an average particle diameter of lOnm was prepared. Five volumes of acetone were added to one volume of this dispersion (colloidal solution) and stirred.
• Fine particles in the dispersion liquid settled out due to the action of polar acetone. After allowing to stand for 2 hours, the supernatant was removed, and the same amount of acetone as the first was added again, followed by stirring. After allowing to stand for 2 hours, the supernatant was removed. The residual solvent was completely removed from the sediment, and In—Sn alloy fine particles having an average particle size of l Onm were produced.
• Fine particles of each metal of In, Sn, Sb, Al, and Zn, and alloy fine particles other than In_Sn, which is a metal force of these metals, can be obtained in the same manner according to the above-described production method.
• In-Sn alloy fine particles produced by evaporation in gas in Production Example 1 were used. These particles had an average particle size of lOnm, and were confirmed to be non-oxidized alloy fine particles by X-ray diffraction. X-ray fluorescence analysis confirmed that the Sn content in the fine particles was 6 wt%.
• oxide fine particles to be combined with the alloy fine particles ITO fine particles having a primary particle of 20 nm were used. These alloy fine particles and ITO fine particles Are mixed and dispersed in an organic solvent (toluene) at a ratio of 5:95 (wt%) to a total solid content of 30 wt% to obtain a dispersion for forming a transparent conductive film.
• organic solvent toluene
• the dispersion obtained by the force was applied onto a glass substrate by spin coating to form a film.
• the resulting coating film baked at a 1 X 10- 3 Pa 230 ° C , 30 minutes condition under a reduced pressure of (1st Aniru) was performed.
• the atmosphere was returned to the atmosphere, and calcination (2nd anneal) at 230 ° C and 10 min was performed in air.
• the obtained transparent conductive film (thickness: 200 nm) was sufficiently densified, and its surface resistance was as low as 60 ⁇ / mouth, and the transmittance at 550 nm was as high as 99.4%.
• firing in a reducing gas atmosphere hydrogen gas atmosphere and carbon monoxide atmosphere
• Example 1 The transparent conductive film obtained in Example 1 was useful as a transparent electrode of a display device.
• Example 1 In-Sn alloy fine particles were removed from the dispersion obtained in Example 1, and a dispersion of only ITO fine particles was applied on a glass substrate in the same manner as in Example 1 to form a dispersion. The membrane was made. Next, the obtained coating film was fired at 230 ° C. for 30 minutes under the same conditions as in Example 1. The resulting transparent conductive film, the transmittance was as high as 98% power its surface resistance 7 ⁇ 10 3 ⁇ / mouth and very Kokaka ivy.
• the metal fine particles having a small particle size fill gaps between the ITO fine particles, and the metal fine particles serve as an adhesive to densify the film. It is presumed that the contact resistance of the fine particles was reduced, resulting in a low-resistance film.
• the concentration of the metal fine particles in all the fine particles is generally about 110 to 30 wt%, preferably about 3 to 30 wt%. It is convenient to From the viewpoint of the cost of the dispersion, the concentration of the metal fine particles is lower, and the more preferable.
• Example 1 calcination was performed according to the method described in Example 1 by changing the types and composition ratios of the metal fine particles and oxide fine particles of each component metal of the metal oxide for forming a transparent conductive film and the calcination conditions. The surface resistance and transmittance of the obtained film were measured. The results are shown in Table 1. Table 1 also shows comparative examples.
• In—Zn alloy fine particles Zn: 6 wt%) and IZO fine particles were used.
• the resistance value was almost the same as that in the case of using the In—Sn alloy fine particles and the ZITO fine particles, and the value was slightly higher, and the transmittance was almost the same as in these cases.
• the resistance value is higher than when using In fine particles or In-Sn alloy fine particles ⁇ fine particles, or when using In-Zn alloy fine particles ⁇ fine particles.
• the transmittance was almost the same as in these cases.
• This film was excellent in thermal stability and chemical stability. No change in resistance was observed even after baking this film at 600 ° C.
• Zn—A1 alloy fine particles (A1: 5 wt%) and AZ ⁇ fine particles were used.
• the resistance value is lower than when using Sn—Sb fine particles / ATO fine particles, and higher than when using In—Sn fine particles / ITO fine particles or In—Zn fine particles / IZO fine particles.
• the force S and the transmittance were almost the same as in these cases.
• Example 47 In fine particles and ATO fine particles were used. In the obtained film, the resistance value and the transmittance were almost the same as those when the Sn—Sb fine particles / ATO fine particles were used.
• Example 48 In—Zn fine particles (Zn: 6 wt%) and ITO fine particles were used. In the obtained film, the resistance value and the transmittance were almost the same as those of the In—Sn fine particles and the ZITO fine particles.
• Example 49 Sn—Sb fine particles (Sb: 5 wt%) and AZ ⁇ fine particles were used.
• the resistance value was higher than that when the Zn-A1 fine particles and the ZAZO fine particles were used, and the transmittance was almost the same.
• Example 50 Zn—A1 fine particles (A1: 5 wt%) and ITO fine particles were used.
• the resistance value was slightly lower than that in the case of using the In—Sn fine particles / ITO fine particles, but the transmittance was almost the same.
• All of the above films had excellent etching characteristics.
• films obtained using In-Zn fine particles and oxide fine particles were composed of In fine particles, In-Sn fine particles or Sn-Sb fine particles and oxides. The etching characteristics were superior to the film obtained using the fine particles. From these facts, it can be seen that the film obtained using the system composed of the In-Zn fine particles and the oxide fine particles is a film excellent in workability.
• a transparent conductive film having low resistance and high transmittance can be formed by firing at a low temperature using a specific dispersion liquid.
• the film can be applied to the field of a transparent conductive film (for example, a transparent electrode) used for a display device such as a flat panel display, a charging of a display surface, and an electromagnetic wave shielding film in a field of, for example, an electric and electronic industry. .

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• Dispersion Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
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• Non-Insulated Conductors (AREA)
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• Inorganic Compounds Of Heavy Metals (AREA)

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