JP4295727B2 - Method for producing a substantially transparent conductive layer - Google Patents

Description

  The present invention relates to a substantially transparent single layer composite conductive layer.

  There is a need for an inexpensive transparent conductive layer in many applications, but for some (large area) applications, a busbar will also be required. Highly conductive (non-transparent) patterns can be produced by screen printing conductive pastes such as silver or carbon black paste. Another method is vacuum deposition of metal through a shadow mask. Yet another method uses a uniform conductive metal treated surface that can be patterned by the use of photoresist technology in combination with a metal etchant. Photographic films can also be used for the production of electrically conductive silver “images” under certain conditions.

  U.S. Pat. No. 6,057,089 describes the use of a photosensitive evaporated silver halide film that forms a conductive image upon exposure and after development. U.S. Patent No. 6,057,031 describes a photographic process for making conductive paths, resistors and capacitors for microcircuits starting from coated silver halide emulsions. Patent document 3 describes the production of an electrically conductive pattern by diffusion transfer technology.

  Combinations of transparent polymer based conductors and highly conductive (non-transparent) patterns have been described in several references. Patent Document 4 discloses an electroluminescent configuration containing a hole and / or electron injection layer, and the polymeric organic conductor is selected from the group of polyfuran, polypyrrole, polyaniline, polythiophene and polypyridine. Yes. Patent Document 4 describes the use of poly (3,4-ethylenedioxythiophene) as a charge injection layer on a transparent metal electrode such as ITO (indium tin oxide), and the following substances: a) metal oxide It also discloses that, for example, ITO, tin oxide, etc .; b) translucent metal films, such as Au, Pt, Ag, Cu, etc. are suitable as transparent and conductive materials. The latter is applied by vacuum technology.

  Patent Document 5 discloses an organic electroluminescent device having an anode, an organic hole injecting / transporting layer, an organic fluorescent layer, and a cathode in this order, where the organic hole injecting / transporting layer is made of an aromatic carboxylic acid. Contains metal complexes and / or metal salts. US Pat. No. 6,057,096 further describes different types of conductivity selected from metals such as Al, Au, Ag, Ni, Pd or Te, metal oxides, carbon black or conductive resins such as poly (3-methylthiophene). It is also disclosed that the conductive layer used in such a device by depositing a material can have a multilayer structure, but the specific combination is not illustrated.

  Patent Document 6 discloses a method for producing a pattern of an electrically conductive polymer on a substrate surface, the method comprising: a) a substance capable of generating the electrically conductive polymer on heating on the surface of the substrate; Forming a liquid layer from a solution containing, for example, 3,4-ethylenedioxythiophene, an oxidant and a base, b) exposing the liquid layer to patterned irradiation, and c) heating the layer; Thereby comprising forming a pattern of electrically conductive polymer, the conductive polymer being formed in the unexposed areas of the layer and the nonconductive polymer being formed in the exposed areas. A galvanic provision of a conductive polymer pattern using a metal layer such as silver, copper, nickel or chromium is also disclosed in US Pat.

  Patent Document 7 describes an organic or organometallic electrically conductive polymer in which the first layer is transparent or translucent in the visible range of the electromagnetic spectrum, such as polythiophene, polythiol, polyaniline, polyacetylene, or those optionally substituted. The second layer may contain at least one electrically conductive inorganic compound or metal or suitably doped metalloid such as Cu, Ag, Au, Pt, Pd, Fe, Cr, Sn, Disclosed is a conductive layer system, in particular for transparent or translucent electrodes or electroluminescent structures, characterized in that it contains a material selected from the group consisting of Al or their alloys or conductive carbon. In a preferred embodiment, the second layer is preferably a conductive pattern formed by an open grid structure with a 5-500 μm grid, so that it cannot be distinguished by the naked eye. Example 2 of the invention is a poly (3,4-ethylene having a surface resistance of 1500 Ω / square applied by printing technology to a conductive track of “Leitsilver” (silver particle dispersion) about 2 mm wide. A dioxythiophene) [PEDOT] / poly (styrene sulfonate) [PSS] layer is disclosed.

  The layer configuration disclosed in Example 2 of Patent Document 7 requires a thickness of 5 to 10 μm of a “late silver” grid in order to obtain a layer having a surface resistance of 0.5 to 1 Ω / square, This has the disadvantage that the surface of the construction has a certain degree of roughness, which limits its use and makes it difficult to apply thin, eg 100 nm, functional layers. Furthermore, aqueous PEDOT / PSS dispersions will not wet such “late silver” grids, and therefore will not result in a multi-layer conductive configuration that can be used.

Furthermore, the use of intrinsic conductor polymer layers or metal grids presents the outermost wetting problem with respect to thin functional layer coatings. Furthermore, for devices that require very thin functional layers, such as transistors, slight deviations from the thinness and flatness of the multilayer electrodes are disadvantageous in their manufacture.
US Pat. No. 3,664,837 German Patent No. 1,938,373 US Pat. No. 3,600,185 German Patent Application Publication No. 196 27 071 European Patent Application Publication No. 510 541 US Pat. No. 5,447,824 WO 98/54767 pamphlet

  Accordingly, one aspect of the present invention provides a conductive electrode having properties similar to, but thinner than, a multilayer electrode comprising a conductive polymer layer and a conductive metal layer with an outermost layer having improved flatness. It is to be.

  Another aspect of the present invention is a method for producing a conductive electrode having properties similar to, but thinner than, a multilayer electrode comprising a conductive polymer layer and a conductive metal layer with an outermost layer having improved flatness. Is to provide.

  Another aspect of the invention is to prevent ion migration from the conductive electrode.

  Other aspects and advantages of the invention will become apparent from the following description.

SUMMARY OF THE INVENTION Intrinsically conductive polymers such as PEDOT / PSS and non-uniformly distributed conductive metals such as silver, which have a high conductivity, such that functional layers can be easily applied, and It has been surprisingly found that a thin substantially transparent conductive layer with an improved planar outermost surface can be realized.

  When a potential is applied under conditions of high relative humidity between the conducting layer according to the invention as a cathode and the reverse electrode as an anode, it always exists in the cathode where there is an equilibrium between metal ions and metal atoms. Metal ions diffuse to the cathode at the applied potential, where they deposit on the metal atoms and deposit the resinous crystalline metal, which grows towards the anode. This creates a long term in the short path of the electrode.

  In the case of a conductive layer containing silver, ions migrate and a silver resinous crystal is formed. The use of benzotriazole as a silver electrode-stabilizer is disclosed in US Pat. No. 4,821,148 and US Pat. No. 6,174,606, and is described by Evenpoel et al. Disclosed the use of thiourea in 1970 in Metallurgie X, volume 4, page 132, and Ambland et al. Disclosed the use of tartaric acid in 1978 in Surface Technology, volume 6, pages 409-423. However, these improved methods have not been successful with the conductive layer of the present invention. Surprisingly, it has been found that certain phenyl-mercaptotetrazole compounds can substantially prevent the formation of silver resinous crystals.

An aspect of the invention is a substantially transparent conductive layer on a support, the layer comprising an intrinsically conductive polymer and a conductive metal, wherein the conductive metal is unevenly distributed therein. And the conductive metal is realized by a conductive layer which itself forms a conductor.

  An aspect of the present invention is a method for producing a substantially transparent conductive layer on a support comprising the step of producing a heterogeneously distributed conductive metal by photographic processing, wherein the layer is intrinsically conductive. This is realized by a method comprising a conductive polymer and the heterogeneously distributed conductive metal therein and forming the conductor by itself.

  Aspects of the invention are also realized by a light emitting diode comprising the above conductive layer or manufactured according to the above method.

  Aspects of the invention are also realized by a photovoltaic device comprising the conductive layer described above or manufactured according to the method described above.

  Aspects of the invention are also realized by a transistor comprising the above conductive layer or manufactured according to the above method.

  Aspects of the invention are also realized by an electroluminescent device comprising the above conductive layer or manufactured according to the above method.

Preferred embodiments are disclosed in the dependent claims.
DETAILED DESCRIPTION OF THE INVENTION FIG. 1 shows four silver patterns, namely a pattern (a) representing a continuous silver layer with an area of 3 × 3 cm ² , regular pieces with parallel pieces 10 mm apart and 1 mm width. A pattern (b) representing a pattern, a pattern (c) representing a regular piece pattern with parallel strips separated by 5 mm and having a width of 150 μm, and a pattern (d) representing no silver development are shown.

Definitions The term alkyl refers to all possible variations for each carbon number in the alkyl group, ie n-propyl and isopropyl for carbon number 3, n-butyl, isobutyl and tertiary-butyl for carbon number 4, Regarding carbon number 5, it means n-pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 2-methyl-butyl and the like.

  The term aqueous for the purposes of the present invention includes the inclusion of at least 60% by volume of water, preferably at least 80% by volume of water, and optionally water-miscible organic solvents such as alcohols such as methanol, ethanol, 2 Means the inclusion of propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol, etc .; glycols such as ethylene glycol; glycerine; N-methylpyrrolidone; methoxypropanol; and ketones such as 2-propanone and 2-butanone To do.

  The term “support” means “self-supporting material” and is distinguished from “layers” which may be coated on the support but which are not themselves self-supporting. It also includes any treatment necessary for adhesion to the support or layers applied to aid it.

  The term continuous layer refers to a layer that covers a whole area of the support and does not necessarily need to be in direct contact with the support.

  The term non-continuous layer refers to a layer where a single surface does not cover the entire area of the support and need not necessarily be in direct contact with the support.

  The term coating refers to all techniques for producing continuous layers, such as curtain coating, doctor-blade coating, etc., and all techniques for producing non-continuous layers, such as screen printing, inkjet printing, flexographic printing, and A generic term that encompasses all means for applying a layer, including techniques for producing a continuous layer.

  The term intrinsically conductive polymer has a (poly) -conjugated π-electron system (eg double bonds, aromatic or heteroaromatic rings or triple bonds) and their conductive properties are eg relative humidity. An organic polymer that is not affected by environmental factors.

The term “conductive” relates to the electrical resistance of a substance. The electrical resistance of the layer is generally indicated by the surface resistance R _S (unit Ω; often expressed as Ω / square). Alternatively, the conductivity is volume resistivity R _v = R _S · d (where d is the thickness of the layer), volume conductivity k _V = 1 / R _v [unit: S (iemens) / cm] or surface Conductance k _S = 1 / R _S [unit: S (iemens). Square] can also be used.

  The term photography refers to any photochemical method, in particular based on the silver halide method.

  The term silver salt diffusion transfer method refers to A. Rott [British Patent No. 614,155 and Sci. Photogr. , (2) 13, 151 (1942)] and E.I. Developed independently by Weyde [DE 973,769] and G.W. I. P. "The Theory of the Photographic Process Fourth Edition" edited by T. Levenson. H. James, pages 466 to 480, Eastman Kodak Company, Rochester (1977).

  The term substantially transparent means that the integral transmission of visible light is above 50% of the standard incident light in the conductive layer of the present invention, i.e. the layer is less than 0.30. The local transmission of visible light through the silver pattern lines that had a density may be well below 10% of the standard incident light in the conductive layer of the present invention, ie an optical density of 1.0 Means it may be much higher.

  The abbreviation PEDOT stands for poly (3,4-ethylenedioxy-thiophene).

  The abbreviation PSS stands for poly (styrene sulfonic acid) or poly (styrene sulfonate).

Conductive layer An aspect of the present invention is a substantially transparent conductive layer on a support, the layer comprising an intrinsically conductive polymer and a conductive metal, wherein the conductive metal is unevenly distributed therein. And the conductive metal is realized by a conductive layer which itself forms a conductor.

  According to a first embodiment of the conductive layer according to the invention, the conductive metal is silver.

Intrinsically Conducting Polymer The intrinsically conducting polymer used in the present invention can be any intrinsically conducting polymer known in the art, such as polyacetylene, polypyrrole, polyaniline, polythiophene, and the like. Details of suitable intrinsic conducting polymers can be found in, for example, “Advanceds in Synthetic Metals”, ed. P. Bernier, S.M. Lefrant, and G.L. Bidan, Elsevier, 1999; “Intrinsically Conducting Polymers: An Emerging Technology”, Kluwer (1993); “Conducting Polymer Fundamentals and AppsAp. Chandrakekhar, Kluwer, 1999; and "Handbook of Organic Conducting Modules and Polymers", Ed. Walwa, Vol. 1-4, Marcel Dekker Inc. It can be seen in textbooks such as (1997).

  According to a second embodiment of the conductive layer according to the invention, the intrinsically conductive polymer is of formula (I):

[Wherein each of R ¹ and R ² independently represents hydrogen or a C _1-4 alkyl group, or together represents an optionally substituted C _1-4 alkylene group or cycloalkylene group. Represent]
The structural unit shown by is contained.

  According to a third embodiment of the conductive layer according to the invention, the intrinsically conductive polymer is a 3,4-dioxy group representing an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted together. It is a polymer or copolymer of alkoxythiophene.

  According to a fourth embodiment of the conductive layer according to the invention, the intrinsically conductive polymer represents an oxy-alkylene-oxy bridge in which two alkoxy groups may be optionally substituted together and poly (3, 4-methylenedioxythiophene), poly (3,4-methylenedioxythiophene) derivative, poly (3,4-ethylenedioxythiophene), poly (3,4-ethylene-dioxythiophene) derivative, poly (3 , 4-propylenedioxy-thiophene), poly (3,4-propylenedioxy-thiophene) derivatives, poly (3,4-butylene-dioxythiophene) and poly (3,4-butylenedioxy-thiophene) derivatives , As well as 3,4-dialkoxythiophene polymers or copolymers thereof.

  According to a fifth embodiment of the conductive layer according to the invention, the intrinsically conductive polymer represents an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted together and represents an oxy-alkylene- Polymers or copolymers of 3,4-dialkoxythiophene where the substituents on the oxy bridge are alkyl, alkoxy, alkyloxyalkyl, carboxy, alkyl sulfonate and carboxy ester groups.

According to a sixth embodiment of the conductive layer according to the invention, the intrinsically conductive polymer represents an oxy-alkylene-oxy bridge in which two alkoxy groups are optionally substituted together and two alkoxy groups. A group together 1,2-ethylene group, an optionally alkyl-substituted methylene group, an optionally C _1-12 alkyl- or phenyl-substituted 1,2-ethylene group, A polymer or copolymer of 3,4-dialkoxythiophene representing an optionally substituted oxy-alkylene-oxy bridge which is a 1,3-propylene group or a 1,2-cyclohexylene group.

  Such polymers are available from Handbook of Oligo- and Polythiophenes Edited by D.D. Fichu, Wiley-VCH, Weinheim (1999); Groendaal et al. in Advanced Materials, volume 12, pages 481-494 (2000); J. et al. Kloepner et al. in Polymer Preprints, volume 40 (2), page 792 (1999); Schottland et al. in Synthetic Metals, volume 101, pages 7-8 (1999); M.M. Welsh et al. in Polymer Preprints, volume 38 (2), page 320 (1997).

Organic polymers containing structural units according to formula (I) can be polymerized chemically or electrochemically. Chemical polymerization can be carried out oxidatively or reductively. For example, J. et al. Amer. Chem. Soc. , Vol. 85, pages 454-458 (1963) and J. Am. Polym. Sci. Part A Polymer Chemistry, vol. 26, pages 1287-1294 (1988), oxidizing agents used for the oxidative polymerization of pyrrole can be used for the oxidative polymerization of thiophenes. According to a seventh aspect of the present invention, an inexpensive and readily available oxidizing agent, such as an iron (III) salt, such as FeCl ₃ , an iron (III) salt of an organic acid, such as Fe (OTs) ₃ , H ₂ O ₂ , K ₂ Cr ₂ O ₇ , alkali and ammonium persulfates, alkali perborates and potassium permanganate are used in the oxidative polymerization.

  Theoretically, oxidative polymerization of thiophenes requires 2.25 equivalents of oxidizing agent per mole of thiophene of formula (I) [see, for example, J. Org. Polym. Sci. Part A Polym. Chem. , Vol. 26, pages 1287-1294 (1988)]. In practice, an excess of 0.1 to 2 equivalents of oxidizing agent is used per polymerizable unit. The use of persulfates and iron (III) salts has the great technical advantage that they do not corrode. Furthermore, in the presence of certain additives, the oxidative polymerization of thiophene compounds according to formula (I) proceeds very slowly, so that thiophenes and oxidants are combined in solution or paste and applied to the substrate to be treated. can do. For example, after application of such a solution or paste, as disclosed in US Pat. No. 6,001,281 and International Publication No. 00/14139, which are incorporated herein by reference. Oxidative polymerization can be accelerated by heating the coated substrate.

  Reductive polymerization was performed in Appperloo et al. Chem. Eur. Journal, volume 8, pages 2384-2396 and disclosed in Tetrahedron Letters, volume 42, pages 155-157 in 2001 and in Organics, volumes 31, volume 31 and pages 2047-2056, respectively. ) Or the Suzuki (organoboron) process or in 1999 in Bull. Chem. Soc. Japan, volume 72, page 621 and nickel complexes disclosed in 1998, Advanced Materials, volume 10, pages 93-116.

1-phenyl-5 substituted with one or more electron accepting groups on the phenyl group
Mercapto-tetrazole compound According to a seventh embodiment of the conductive layer according to the present invention, the conductive layer further contains a silver-ion stabilizer.

  According to an eighth aspect of the conductive layer according to the present invention, the silver-ion stabilizer is a 1-phenyl-5-mercapto-tetrazole compound in which the conductive group is substituted with one or more electron accepting groups. Is further contained.

  According to a ninth aspect of the conductive layer according to the invention, the conductive layer has one or more electron accepting groups wherein the phenyl group is selected from the group consisting of chloride, fluoride, cyano, sulfonyl, nitro, acid amide and acylamino groups. It further contains a silver-ion stabilizer which is a 1-phenyl-5-mercapto-tetrazole compound substituted with a group.

  According to a tenth aspect of the conductive layer according to the present invention, the conductive layer is 1- (3 ', 4'-dichlorophenyl) -5-mercapto-tetrazole,

It further contains a silver-ion stabilizer selected from the group consisting of:

  Suitable 1-phenyl-5-mercapto-tetrazole compounds [PMT] having a substituted phenyl group according to the present invention include:

Method for Producing Conductive Layer An aspect of the present invention is also a method for producing a substantially transparent conductive layer on a support comprising the step of producing a non-uniformly distributed conductive metal by photographic processing. This layer is also realized by a method comprising an intrinsically conductive polymer and the non-uniformly distributed conductive metal therein and forming the conductor itself.

  According to a first embodiment of the method according to the invention, the photographic processing is performed by coating the support with a layer containing an intrinsic conducting polymer and a nucleating agent and using a silver salt diffusion transfer to discontinuously in the nucleation layer. Forming a silver layer.

  According to a second embodiment of the method according to the invention, the photographic processing comprises coating the support with a layer containing an intrinsic conducting polymer and palladium sulfide as a nucleating agent, for example palladium sulfide nanoparticles, and carrying out silver salt diffusion transfer. Using to produce a discontinuous silver layer in the nucleation layer.

  According to a third embodiment of the method according to the present invention, the photographic processing comprises the support as an intrinsically conductive polymer, silver halide and gelatin in a weight ratio of gelatin to silver halide in the range of 0.05 to 0.3. Coating with the containing layer, exposing the layer imagewise, and developing the exposed layer to produce a non-uniformly distributed silver.

Surfactant According to an eleventh aspect of the conductive layer according to the present invention, the conductive layer further comprises a surfactant.

  According to a twelfth aspect of the conductive layer according to the present invention, the conductive layer is a nonionic surfactant, such as an ethoxylated / fluoro-alkyl surfactant, a polyethoxylated silicone surfactant, a polysiloxane / It further comprises a polyether surfactant, an ammonium salt of perfluoro-alkyl carboxylic acid, a polyethoxylated surfactant and a fluorine-containing surfactant.

Suitable nonionic surfactants include the following:
Surfactant number 01 = ZONYL ^™ FSN from DuPont, F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ O (CH ₂ CH ₂ O) in a 50 wt% solution of isopropanol in water _x H [wherein, x = 0 to about 25] 40 wt% solution of;
Surfactant number 02 = Zonyl ^™ FSN-100 from DuPont: F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ O (CH ₂ CH ₂ O) _x H, where x = 0 to about 25 is there];
Surfactant No. 03 = Zonyl ^TM FS300 from DuPont, 40 wt% aqueous solution of fluorinated surfactant;
Surfactant No. 04 = Zonyl ^™ FSO from DuPont, Formula F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H in a 50 wt% solution of ethylene glycol in water [Formula In which y = 0 to about 15] a 50 wt% solution of a mixture of ethoxylated nonionic fluoro-surfactants;
Surfactant No. 05 = Zonyl ^TM FSO-100 from DuPont, Formula F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O (CH ₂ CH ₂ O) _y H [where y = 0 to about 15 A mixture of ethoxylated nonionic fluoro-surfactants from DuPont with
Surfactant No. 06 = Tegoglide ^™ 410 from Goldschmidt, polysiloxane-polymer copolymer surfactant;
Surfactant No. 07 = Tegowet ^™ from Goldschmidt, polysiloxane-polyester copolymer surfactant;
Surfactant Nr 08 = Fluorad from _{^{3M (FLUORAD) TM FC431: CF}} 3 (CF 2) 7 SO 2 (C 2 H 5) N-CH 2 CO- (OCH 2 CH 2) n OH;
Surfactant number 09 = Fluorad ^™ FC126 from 3M, mixture of ammonium salts of perfluorocarboxylic acid;
Surfactant No. 10 = Polyoxyethylene-10-lauryl ether Surfactant No. 11 = Fluorad ^™ FC430 from 3M, 98.5% active fluoroaliphatic ester;
According to a thirteenth aspect of the conductive layer according to the present invention, the conductive layer further contains an anionic surfactant.

Suitable anionic surfactants include the following:
Surfactant No. 12 = Zonyl ^TM 7950 from DuPont, fluorinated surfactant;
Surfactant No. 13 = Zonyl ^™ FSA from DuPont, F (CF ₂ CF ₂ ) _1-9 CH ₂ CH ₂ SCH ₂ CH ₂ COOLi in a 50 wt% solution of isopropanol in water;
Surfactant No. 14 = Zonyl ^TM FSE from DuPont, [F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (ONH ₄ ) _y in 70 wt% aqueous ethylene glycol solution In which x = 1 or 2, y = 2 or 1, and x + y = 3];
Surfactant No. 15 = Zonyl ^TM FSJ from DuPont, F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (ONH ₄ ) _{y in a} 25 wt% solution of isopropanol in water In which x = 1 or 2, y = 2 or 1, and x + y = 3] and a 40% by weight solution of a blend of hydrocarbon surfactants;
Surfactant No. 16 = Zonyl ^™ FSP from DuPont, [F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (ONH ₄ ) in a 69.2 wt% solution of isopropanol in water _y [wherein a x = 1 or 2, y = 2 or 1, and x + y = 3 is a] 35 wt% solution of;
Surfactant number 17 = Zonyl ^TM UR from DuPont: [F (CF ₂ CF ₂ ) _1-7 CH ₂ CH ₂ O] _x P (O) (OH) _y [wherein x = 1 or 2 Y = 2 or 1 and x + y = 3];
Surfactant No. 18 = Zonyl ^™ TBS from DuPont, 33 wt% solution of F (CF ₂ CF ₂ ) _3-8 CH ₂ CH ₂ SO ₃ H in 4.5 wt% solution of acetic acid in water;
Surfactant No. 19 = Perfluoro-octanoic acid ammonium salt from 3M
Binder According to a fourteenth embodiment of the conductive layer according to the present invention, the conductive layer further contains a binder.

Crosslinker According to the fifteenth embodiment of the conductive layer according to the present invention, the conductive layer further contains a crosslinker.

Support According to a sixteenth embodiment of the conductive layer according to the present invention, the support is transparent or translucent.

  According to a seventeenth aspect of the conductive layer according to the invention, the support is polymer film, silicon, ceramic, oxide, glass, polymer film tempered glass, glass / plastic laminate, metal / plastic laminate, optionally treated. Paper and laminated paper that may be included.

  According to an eighteenth embodiment of the conductive layer according to the present invention, the support is provided with other adhesion promoting means to aid adhesion to the subbing layer or the substantially transparent conductive layer.

  According to a nineteenth embodiment of the conductive layer according to the present invention, the support is a transparent or translucent polymer film.

  Transparent or translucent supports suitable for use with the electrically conductive layer or antistatic layer according to the present invention may be hard or soft and glass, glass-polymer laminates, polymer laminates, thermoplastic polymers Alternatively, it can be made of a juroplastic polymer. Examples of thin soft supports are cellulose esters, cellulose triacetate, polypropylene, polycarbonate or polyester, poly (ethylene terephthalate), which may optionally be treated by corona discharge or glow discharge or may be provided with an undercoat layer , Poly (ethylene naphthalene-1,4-dicarboxylate), polystyrene, polyethersulfone, polycarbonate, polyacrylate, polyamide, polyimides, cellulose triacetate, polyolefins and poly (vinyl chloride). .

Electroluminescent Device Aspects of the present invention are also realized by an electroluminescent device comprising a conductive layer according to the present invention or manufactured by a manufacturing method according to the present invention.

  Thin film electroluminescent devices (ELDs) are all characterized by one (or more) electroluminescent active layers sandwiched between two electrodes. In some cases, the dielectric layer may be part of a sandwich.

  Thin film ELDs can be subdivided into organic and inorganic based ELDs. Organic-based thin film ELDs can be subdivided into low molecular weight organic devices (organic light emitting diode (OLED)) and oligomeric organic devices (polymer light emitting diode (PLED)), including oligomers. On the other hand, inorganic ELDs can be further subdivided into high voltage alternating current (HV-AC) ELD and low voltage direct current (LV-DC) ELD. LV-DC ELDs include powder ELDs (DC-PEL devices or DC-PELD) and thin film DCC-ELDs, hereinafter referred to as inorganic light emitting diodes (ILEDs).

  The basic structure of an organic ELD (PLED and OLED) comprises the following layer arrangement: a transparent substrate (glass or soft plastic), a transparent conductor such as indium tin oxide (ITO), a hole transport layer, fluorescence Layer, and a second electrode, such as a Ca, Mg / Ag or Al / Li electrode. For OLEDs, the hole transport and phosphor layers are 10-50 nm thick and are applied by vacuum deposition, whereas for PLEDs, the hole transport layer is typically about 40 nm thick and the phosphor layer is typically about 100 nm thick. And applied by spin coating or other non-vacuum coating techniques. An energy for applying a DC voltage of 5-10 V between the electrodes and emitting light from the holes and injecting electrons from the positive and negative electrodes, respectively, to combine in the fluorescent layer and thereby excite the fluorescent species. To emit light.

  In the OLED, the hole transport layer and the electroluminescent layer are made of a low molecular weight organic compound, and for example, N, N′-diphenyl-1,1′-biphenyl-4,4′-diamine is used as the hole transporter. And aluminum (III) 8-hydroxyquinoline complexes, polyaromatics (anthracene, perylene and stilbene derivatives) and polyheteroaromatics (oxazole, oxadiazole, thiazole, etc.) can be used as electroluminescent devices it can.

  For PLEDs, the electroluminescent compounds that can be used are polymers such as non-conjugated poly (N-vinylcarbazole) derivatives (PVK) or poly (p-phenylene vinylene) (PPV), polyfluorene, poly (3-alkylthiophene). And conjugated polymers such as poly (p-phenyleneethynylene).

  A low voltage DC PEL device generally comprises a transparent substrate, a transparent conductor (ITO), a doped ZnS phosphor layer (20 μm), and a top electrode of evaporated aluminum. The phosphor layer is applied by evaporation onto the ITO conductive layer by doctor blade technology or screen printing technology. When a direct voltage of several volts (ITO positive) is applied, the holes move toward the aluminum electrode, thereby creating an insulating region (thickness about 1 μm) next to the ITO layer within about 1 minute. This results in a current drop that is associated with the onset of light emission. This method has been referred to as the forming process. In the thin high-resistance phosphor layer formed thereby, a high electric field is generated and electroluminescence can already occur at low voltages (typically between 10-30V).

  In hybrid LEDs, so-called quantum dots that are inorganic luminescent are used in combination with organic polymers having charge transport properties and in some cases luminescent properties. Hybrid LEDs with CdSe nanoparticles are described in Colvin et al., Which is incorporated herein by reference. [See Nature, volume 370, pages 354-357, (1994)], Dabbousi et al. [Appl. Phys. Lett. , Volume 66, pages 1316-1318 (1995)], and Gao et al. [J. Phys. Chem. B, volume 102, pages 4096-4103 (1998)].

  A light-emitting device having ZnS: Cu nanocrystals and a non-conducting polymer operating at a voltage lower than 5 V is disclosed in Huang et al., Which is incorporated herein by reference. [Appl. Phys. Lett. , Volume 70, pages 2335-2337 (1997)] and Que et al. Appl. Phys. Lett. , Volume 73, pages 2727-2729 [1998]].

  According to a first embodiment of the electroluminescent device according to the invention, the electroluminescent device is a light emitting diode.

  According to a second embodiment of the electroluminescent device according to the invention, the electroluminescent device further comprises a layer of electroluminescent phosphor.

  According to a third embodiment of the electroluminescent device according to the invention, the electroluminescent device further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor is a II-VI group semiconductor, for example ZnS, or a combination of a group II element and an oxidizing anion, which is a silicate, phosphate, carbonate, germanate, stannate, borate, vanadate, tungstate and oxy Sulfate is the most universal. Typical dopants are metals and all rare earths such as Cu, Ag, Mn, Eu, Sm, Tb and Ce.

According to a fourth embodiment of the electroluminescent device according to the invention, the electroluminescent device further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor is a transparent moisture barrier layer, for example Al. Encapsulated with ₂ O ₃ and AlN. Such phosphors are available from Sylvania, Shinetsu Polymer KK, Dural, Acheson, and Toshiba. Examples of coatings using such phosphors are the 72X available from Sylvania / GTE and the coating disclosed in US Pat. No. 4,855,189.

According to a fifth aspect of the electroluminescent device according to the invention, the electroluminescent device further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor is doped with manganese, copper or terbium. ZnS or cerium-doped CaGa ₂ S ₄ , for example, electroluminescent phosphor paste supplied by DuPont: LUXPRINT ^TM type 7138J, a white phosphor, lux, a green-blue phosphor is a well electro Doug ^(ELECTRODAG) supplied by Acheson TM EL-035A; Print ^TM type 7151J; and yellow-green Irohotaru lux printing ^TM type is phosphor 7174J.

  According to a sixth embodiment of the electroluminescent device according to the invention, the electroluminescent device further comprises a layer of electroluminescent phosphor, wherein the electroluminescent phosphor is doped with manganese and encapsulated with AlN. Zinc sulfide phosphor.

  According to a seventh embodiment of the electroluminescent device according to the invention, the electroluminescent device further comprises a dielectric layer.

Any dielectric material can be used in the dielectric layer, such as yttria titanate and barium, for example Luxprint ^TM type 7153E high-K dielectric insulator supplied by DuPont and titanium supplied by Acheson. Electrodag ^TM EL-040, which is a barium acid paste, is preferred. A positive ion exchanger can be added in the dielectric layer to trap soluble ions that escape from the phosphor in the luminescent layer. The amount of exchanger in the dielectric layer should be optimized so that it does not reduce the initial brightness level while having the greatest effect on sunspot reduction. Therefore, it is preferable to add 0.5 to 50 parts by weight of the ion exchanger to 100 parts by weight of the total amount of resin and dielectric material in the dielectric layer. The ion exchanger can be organic or inorganic.

  Suitable inorganic ion exchangers are hydrated antimony pentoxide powder, titanium phosphate, phosphoric acid and silicic acid salts, and zeolites.

  Aspects of the invention are also realized by a light emitting diode comprising the above conductive layer or manufactured according to the above method.

  According to a first embodiment of the light emitting diode according to the invention, the light emitting diode further comprises an electroluminescent layer comprising a low molecular weight electroluminescent compound.

  According to a second embodiment of the light emitting diode according to the invention, the light emitting diode further comprises an electroluminescent layer comprising a polymeric electroluminescent compound.

  According to a third embodiment of the light emitting diode according to the invention, the light emitting diode further comprises an electroluminescent quantum short point.

Photovoltaic Device Aspects of the invention are also realized by a photovoltaic device comprising a conductive layer according to the invention or manufactured according to a method according to the invention.

  Aspects of the invention are also realized by a solar cell comprising a conductive layer according to the invention or manufactured according to a method according to the invention.

  According to the first aspect of the photovoltaic cell device according to the present invention, the photovoltaic cell device further comprises at least one photovoltaic cell layer. The photovoltaic layer can be an organic layer, a hybrid inorganic and organic layer or an inorganic layer.

  Photovoltaic devices incorporating a conductive layer according to the present invention are of two types: current carrying electrons are transferred to the anode and external circuitry and holes are transferred to the cathode without converting the light into electrical power and leaving a substantial chemical change. Regenerative types where they are oxidized by electrons from the external circuit, as well as one reacts with holes on the surface of the semiconductor electrode and one with electrons entering the reverse electrode, eg water is oxidized at the semiconductor photoanode and It can be a photosynthetic type with two redox systems that are reduced to hydrogen at the cathode. In the case of the photovoltaic cell regeneration type exemplified by the Graetzel cell, the electron transport medium is a nanoporous metal oxide semiconductor having a band-gap greater than 2.9 eV, such as titanium dioxide, niobium oxide (V ), Tantalum (V) and zinc oxide, the hole transport medium being a liquid electrolyte that aids the redox reaction, a gel electrolyte that aids the redox reaction, a low molecular weight material such as 2,2 ′, 7,7 ′ -In tetrakis (N, N-di-p-methoxyphenyl-amine) 9,9'-spirobifluorene (OMeTAD) or triphenylamine compounds or polymers such as PPV-derivatives, poly (N-vinylcarbazole) etc. Possible organic hole transport material, or an inorganic semiconductor such as CuI, CuSCN, etc. Kill. The charge transfer method can be ionic as in the case of liquid or gel electrolytes, or it can be electronic as in the case of organic or inorganic hole transport materials.

  Such a regenerative photovoltaic cell device can have various internal structures according to the end use. The possible forms are roughly classified into two types: structures that receive light from both sides and those that receive light from one side. Examples of the former are transparent conductive layers, such as ITO-layers or PEDOT / PSS-containing layers and transparent reverse electrode electrically conductive layers, such as ITO-layers or PEDOTs having a sandwiched photosensitive layer and charge transport layer This is a structure manufactured from a / PSS-containing layer. Such devices preferably have their sides sealed with polymers, adhesives, etc. to prevent degradation or volatilization of internal materials. External circuits connected to the electrically conductive substrate and the counter electrode by respective conductors are known.

Alternatively, spectrally sensitized nano-porous metal oxides according to the present invention were prepared in 1991 by Graetzel et al. In Nature, volume 353, pages 737-740, U.S.A. in 1998. Bach et al. [See Nature, volume 395, pages 83-585 (1998)], and in 2002. U. Huynh et al. [See Science, volume 295, pages 2425-2427 (2002)]. In all these cases, at least one of the components (light absorber, electron transfer agent or hole transfer agent) is inorganic (eg nano-TiO ₂ as electron transfer agent, light absorber and electron transfer agent) And at least one of the components is organic (eg, triphenylamine as a hole transfer agent or poly (3-hexylthiophene) as a hole transfer agent).

Transistors Aspects of the invention are also realized by a transistor comprising a conductive layer according to the invention or manufactured according to a method according to the invention.

  According to a first embodiment of the transistor according to the invention, the transistor further comprises a layer having one or more of the electron transport or hole transport components described above, but in a configuration that can be used as a transistor. Become. The semiconductor can be n-type, p-type or both (ambipolar transistors) and can be either organic or inorganic.

Industrial applications Conductive layers according to the invention are used for a wide range of electronic devices such as photovoltaic devices, solar cells, batteries, capacitors, light emitting diodes, organic and inorganic electroluminescent devices, smart windows, electrochromic devices, organic and bio-organic materials. As well as field effect transistors [Handbook of Oligo- and Polythiophenes, Edited by D.D. See also Chapter 10 of Fichu, Wiley-VCH, Heinheim (1999)].

  The present invention will be described below with reference to examples of the present invention and comparative examples. The percentages and ratios indicated in these examples are by weight unless otherwise indicated.

  Ingredients used in the comparative experiment of Example 2:

Example 1 [Comparative Example]
Production of conductive Ag-pattern material A produced by diffusion transfer reaction with conductive PEDOT / PSS on top:
The production of physical development nuclei (PdS) is described in the examples of EP 0 769 723. From this example, nuclei were prepared using solutions A1, B1 and C1. To 1000 mL of this PdS dispersion, 10 g of a 10 g / L aqueous solution of Aerosol OT from American Cyanamid and 5 g of a 50 g / L solution of perfluorocaprylamido-polyglycol were added. This dispersion was then coated onto a poly (ethylene terephthalate) support having a 4 μm thick gelatin subbing layer to a wet layer thickness of 13.5 μm and then dried at 25 ° C. for 60 minutes. This is material A.
Production of PEDOT / PSS dispersions EP 686662 and US Pat. No. 5,766,515 disclose in the examples the production of 1.2% PEDOT / PSS dispersions in water. Yes. 15 mL Zonyl ^™ FSO100 2% aqueous solution, 1.25 g Z6040 silane from Dow Corning and 25 g diethylene glycol are added to 106 g of this dispersion and PEDOT / PSS used in the following examples A dispersion was given.
Production of material B:
Material A was coated to a wet thickness of 40 μm using the PEDOT / PSS dispersion described above and then dried at 100 ° C. for 15 minutes, thereby producing Material C.
Production of transfer emulsion layer:
Manufacturing production and transfer emulsion layer chloro silver bromide emulsion, except that the coverage of the applied silver halide corresponded to AgNO ₃ of 1.25 g / ^{m 2} in place of 2 g / ^{m 2,} the European Patent This was as disclosed in Japanese Patent Application No. 769723.
Exposure and development of materials A and B:
The transfer emulsion layer is image-wise exposed as shown in FIG. 1 and contacted with a receiver (Material A and Material B) at 25 ° C. for 10 seconds at AGFA-GEVAERT ^™ CP297 developer Processed with solution.
Manufacture of double layer electrode configuration:
Treated material A was coated with the PEDOT / PSS-dispersion described above to a wet layer thickness of 50 μm and then dried at 120 ° C. for 20 minutes. The surface resistance of the PEDOT / PSS layer was about 500 Ω / square in the unexposed region of Material A. Material C was thereby produced.
Evaluation of materials B and C:
Surface resistance measurements were performed as follows: the layer electrode configuration can be cut into 3.5 cm wide pieces to ensure complete placement of the electrode material, line contact can be produced, and TEFLON The contact area of 3.5 × 3.5 cm ² is obtained by bringing parallel copper electrodes, each 35 mm long and 3 mm wide and 35 mm apart, placed on the ^TM insulator into contact with the outermost conductive layer of the piece. A constant contact force was ensured by placing a 4 kg weight on a Teflon ^™ platform, and the surface resistance was then measured directly using a Fluke-77III multimeter.

The optical density of the conductive layer is, as for the conductive layer without photographic processing, the pattern type (d) where silver was not developed and the pattern type where silver was developed over the entire 3 cm × 3 cm area without subtracting the density of the support ( In a), the transmittance was measured using a MacBeth ^™ TD924 densitometer with a visible filter. Table 1 shows the surface resistance and optical density (finished material) after exposure and development according to the pattern shown in FIG.

Example 2 (Invention)
Production of palladium sulfide dispersion:
The production of physical development nuclei (PdS) is described in the examples of EP 0 769 723. From this example, nuclei were prepared using solutions A1, B1 and C1.
Production of material D:
100 g of the above PEDOT / PSS dispersion was mixed with 3.35 g of PdS-dispersion. To this mixture was added 1.25 g of Aerosol ^™ OT (American Cyanamide) 10 g / L aqueous solution, 0.625 g of a perfluorocaprylamide-polyglycol 50 g / L solution and 61.9 ml of water to form a coating dispersion. Gave. This dispersion is coated onto a support consisting of a poly (ethylene terephthalate) film and a 4 μm thick gelatin subbing layer using a doctor blade to a wet layer thickness of 50 μm and then dried at 100 ° C. for 15 minutes. Material D was manufactured.
Production of transfer emulsion layer:
Manufacturing production and transfer emulsion layer chloro silver bromide emulsion, except that the coverage of the applied silver halide corresponded to AgNO ₃ of 1.25 g / ^{m 2} in place of 2 g / ^{m 2,} the European Patent This was as disclosed in Japanese Patent Application No. 769723.
Exposure and Development The transferred emulsion layer was image-wise exposed as shown in FIG. 1 and processed with Agfa-Gebert ^™ CP297 developer solution at 25 ° C. for 10 seconds in contact with the receiver.
Evaluation Surface resistance and optical density measurements were performed as described above for Comparative Example 1 and the results are shown in Table 2.

  Comparing Tables 1 and 2, the surface resistance and optical density measured using the inventive single layer composite of material D are completely the same as the bi-layer configuration of material B having the same components manufactured using the same technique. It is astonishing that the PEDOT / PSS-layers were comparable to and exhibited a higher visible light transmission than the bilayer construction of material C coated on a discontinuous developed silver layer.

  Embedding the developed silver in the PEDOT / PSS-layer results in a greater flatness of the outermost surface of the silver layer compared to the bilayer configuration.

From Table 2, it can be seen that (1) the PEDOT / PSS layer can be exposed to Agfa-Gebert ^{™ TM} CP297 developer with only a small loss in surface conductivity without affecting optical clarity, and (2) the same components It can be concluded that the developed silver embedded with the silver-line significantly increasing the “apparent” surface conductivity, as in the case of a two-layer configuration with, forms a conductor by itself.

Example 3 (Invention)
A conceptual experiment was conducted using a recorder film having a gelatin to silver ratio of 0.014. The exposed area of 1 × 3 cm ² as an electrode having a 40 μm separation gave a conductive silver pattern by processing with conventional graphic processing. The resulting electrode pattern had a surface resistance of 50-100 ohms / square.

  The electrodes were conditioned for 3 days at 35 ° C. and 80% relative humidity. Table 3 lists the aqueous solutions used to treat the electrodes before applying a 100 V potential between adjacent electrodes.

  After treatment of the electrodes by immersion in solution at 25 ° C. for 1 minute, a potential of 100 V was applied between adjacent electrodes for 20 minutes. The results were observed under a microscope and photographed. The gap between the electrodes without pretreatment and before applying the potential was measured to be 43.0 ± 0.7 μm. Tables 4 and 5 show the final gap width and specific pretreatment and subsequent silver resin after application of 100 V potential over 20 minutes for comparative experiments using STAB01-STAB09 and experiments of the present invention using PMT01-PMT14, respectively. General observations regarding the formation of glassy crystals are recorded.

  These results show the migration of silver ions upon conditioning at 35 ° C. and 80% relative humidity for 3 days and subsequent application of a 100 V DC potential for 20 minutes without pretreatment (Comparative Experiments 2 and 3). A comparison of the results for Comparative Experiments 1 and 2 shows that conditioning clearly promoted silver resinous crystal growth as observed in the actual apparatus.

  Pretreatment with an aqueous solution of sodium tartrate (STAB02) gave limited inhibition as shown by the reduced growth of the silver resinous crystal front. Pretreatment with high concentration sodium sulfide (STAB04) seemed to peel the silver resinous crystal front from the electrode. Low concentrations of 5-methyl-s-triazolo [1,5-a] pyrimidin-7-ol (STAB05) also grow silver resinous crystals as evidenced by decomposition of the silver resinous crystal front into silver resinous groups. This was limited to a specific area.

With the notable exception of unsubstituted 1-phenyl-5-mercapto-tetrazole [STAB01], all tested 5-mercapto-tetrazoles are at least the appearance of a destroyed front formed by silver resinous crystals. As can be seen, at least limited suppression was also given to the silver resinous crystal forming step. 1-Phenyl-5-mercapto-tetrazole itself showed this performance in the presence of the surfactant, Antarox ^™ CO630, a nonionic surfactant. However, the 1-phenyl-5-mercapto-tetrazole compound having a phenyl group substituted with at least one electron-accepting group, such as a halide, acylamino or amide group, as shown by compounds PMT01-PMT14 is substantially Only suppression was observed. Nearly complete inhibition was observed with pretreatment using solutions 29, 30, 31, 39, 43, 44, 46, 51, 54 and 60, ie with pretreatment using PMT1, PMT05, PMT06, PMT08, PMT09 and PMT12. Nearly complete inhibition was observed at concentrations of 0.005% or lower of 1-phenyl-5-mercapto-tetrazole having a phenyl group substituted with an electron accepting group.

  The invention may encompass any general matter whether or not related to any feature or combination of features explicitly or explicitly disclosed herein or whether it relates to the claimed invention. . In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.

FIG. 1 shows four silver patterns, namely a pattern (a) representing a continuous silver layer with an area of 3 × 3 cm 2, a pattern representing a regular piece pattern with parallel pieces 10 mm apart and a width of 1 mm (b) ), A pattern (c) representing a regular strip pattern with parallel strips 5 mm apart and having a width of 150 μm, and a pattern (d) representing no silver development.

Claims (6)

A substantially transparent conductive layer on a support, conductive layer comprising a conductive silver pattern said layer to form an intrinsic conductive polymer and conductor itself. A method of manufacturing a intrinsically conductive polymer and a substantially transparent conductive layer comprising a conductive silver pattern that forms a conductor by itself on a support, prepared by photographic processing said silver pattern A method comprising steps. Intrinsically conductive polymer and comprising a conductive silver pattern that forms a conductor by itself, or a substantially transparent conductive layer on a support consisting Nde contains, or intrinsically conductive polymers and itself a method for producing a substantially transparent conductive layer comprising a conductive silver pattern that forms a conductor on a support, is prepared by a process comprising the step of producing the photographic processing the silver pattern A light emitting diode comprising a conductive layer . Intrinsically conductive polymer and comprising a conductive silver pattern that forms a conductor by itself, or a substantially transparent conductive layer on a support consisting Nde contains, or intrinsically conductive polymers and itself a method for producing a substantially transparent conductive layer comprising a conductive silver pattern that forms a conductor on a support, by a process comprising the step of producing the photographic processing said conductive silver pattern Photovoltaic device comprising a conductive layer to be manufactured. Intrinsically conductive polymer and comprising a conductive silver pattern that forms a conductor by itself, or a substantially transparent conductive layer on a support consisting Nde contains, or intrinsically conductive polymers and itself a method for producing a substantially transparent conductive layer comprising a conductive silver pattern that forms a conductor on a support, by a process comprising the step of producing the photographic processing said conductive silver pattern A transistor comprising a conductive layer to be manufactured. Intrinsically conductive polymer and comprising a conductive silver pattern that forms a conductor by itself, or a substantially transparent conductive layer on a support consisting Nde contains, or intrinsically conductive polymers and itself a method for producing a substantially transparent conductive layer comprising a conductive silver pattern that forms a conductor on a support, by a process comprising the step of producing the photographic processing said conductive silver pattern An electroluminescent device comprising a conductive layer to be manufactured.

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