CN104981427A - Fine copper nitride particles and production method therefor - Google Patents
Fine copper nitride particles and production method therefor Download PDFInfo
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- CN104981427A CN104981427A CN201480006826.7A CN201480006826A CN104981427A CN 104981427 A CN104981427 A CN 104981427A CN 201480006826 A CN201480006826 A CN 201480006826A CN 104981427 A CN104981427 A CN 104981427A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0625—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with copper
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4417—Methods specially adapted for coating powder
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The purpose of the present invention is to provide fine copper nitride particles that decompose into copper and nitrogen at temperatures of 300 DEG C or less. The present invention relates to fine copper nitride particles that are essentially free from the instability of metallic copper and problems related to high-temperature treatment, and a production method for the fine copper nitride particles. The fine copper nitride particles have a primary particle size of 1-100 nm and a decomposition temperature of 300 DEG C or less. It is preferable that the secondary particle size be 1 [mu]m or less.
Description
Technical field
The present invention relates to distribution ink material and the printing base of copper nitride particulate and manufacture method and use copper nitride particulate.
Background technology
In recent years, as reducing, necessary operation quantity is formed for the pattern of electron device, a large amount of production can be realized, the distribution of cost degradation, the forming method of electrode film, the printed electronic device technology adopting silk screen printing or ink jet method to form Wiring pattern is developed, accompany therewith, the metal wiring material of one of the core material as this technology is studied energetically.At present, be studied centered by Nano silver grain, but because the ion transport of silver is high, price is high, so attempt using the wiring method that should be able to solve the copper nano-particle of this problem.But copper is not only easily oxidized, unstable, and in order to present electroconductibility, also need to process under the high temperature after printing more than 350 DEG C, therefore can not on the polymeric substrate such as polyimide or polyethylene terephthalate distribution.Like this, some problems that overcome to also be there are by practical for the printed wiring of copper.
At present, the research relating to copper nitride crystal is carried out studying (non-patent literature 1) for the purpose of material with memory purposes.
In addition, because copper nitride crystal has scale resistance, so it can be used as the oxide-resistant film of metallic copper to be prepared, the patent relating to its method for making is applied (patent documentation 1, patent documentation 2).
The previous methods preparing these copper nitrides mainly utilizes solid state reaction, under making inorganic mantoquita, the metallic copper high temperature such as copper chalcogenide, contact ammonia, and then preparation (non-patent literature 2).
About the liquid phase synthesis of copper nitride particulate, as described in non-patent literature 3, using the inorganic salt of sodiumazide and copper as raw material, in toluene solvant, use pressure vessel, at spontaneous heating under pressure, can copper nitride be synthesized.But due to the required pressure vessel of such manufacture method, need the tight management to temperature of reaction and pressure, there is the danger of blast, therefore not talkative is very easy method.
In addition, in method shown in non-patent literature 4, to comprise the compound of nitrogen-atoms as solvent, show the reaction under normal pressure.But, in this document, use high boiling stearylamine (air pressure is boiling point 232 DEG C under 32mmHg) as solvent and coating materials, to be 280 DEG C with temperature of reaction and to react.Because remaining a large amount of high boiling coating materials on the copper nitride particle surface that document obtains thus, so be inappropriate for the low temperature distribution material of one of object of utilizing of copper nitride particulate.
At first technical literature
Patent documentation
Patent documentation 1: Japanese Patent No. 3870273 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-12339 publication
Non-patent literature
Non-patent literature 1:Japanese Journal of Applied Physics, 1990,29,1985-1986.
Non-patent literature 2:Solid State Science, 2007,9,907-913.
Non-patent literature 3:Inorganic Chemistry, 2005,44,7385-7393.
Non-patent literature 4:Chemical Communications, 2012,47,3604-3606.
Summary of the invention
In view of above-mentioned prior art, the object of the invention is to, develop the copper nitride particulate that less than 300 DEG C resolve into copper and nitrogen, even if do not adopt pressure treatment or vacuum-treat, also effectively can obtain copper nitride particulate.The present invention relates to the copper nitride particulate in essence without the instability of metallic copper, the problem of pyroprocessing, and its manufacture method.
Copper nitride has scale resistance, and becoming at bulk state, the temperature of less than 350 DEG C to resolve into copper and nitrogen, generation metallic copper, this is as you know, and the present inventor etc. notice that it is the material of the shortcoming of solution metallic copper.So, the present inventor etc. are in order to solve above-mentioned problem, conduct in-depth research, found that the compound that makes to become copper source and become the compound coexist of nitrogenous source in organic solvent, heat, can prepare the copper nitride particulate that primary particle size is below 100nm thus, the decomposition temperature of the copper nitride particulate obtained is less than 300 DEG C, thus completes the present invention.
Namely, the present invention in order to solve the problem, following invention is provided.
[1] a copper nitride particulate, the particle diameter of primary particle is 1 ~ 100nm, and decomposition temperature is less than 300 DEG C.
[2] the copper nitride particulate according to above-mentioned [1], the particle diameter of offspring is less than 1 μm.
[3] the copper nitride particulate according to above-mentioned [1] or [2], in differential thermal balance is analyzed, has the decomposition temperature of adjoint weight minimizing the scopes of 70 DEG C ~ 300 DEG C.
[4] the copper nitride particulate according to any one in above-mentioned [1] ~ [3], in electron microscope observation, secondary particle is spherical.
[5] the copper nitride particulate according to any one in above-mentioned [1] ~ [4], in powder x-ray diffraction, in any one region of 21.5 ~ 24.5 ° under CuK α line, 31.0 ~ 34.0 °, 39.0 ~ 42.0 ° and 46.0 ~ 49.0 °, there is the diffraction peak that at least more than one derives from copper nitride.
[6] a kind of manufacture method of copper nitride particulate; it is characterized in that, by copper source and nitrogenous source, or copper source, nitrogenous source and protective material dissolve or are scattered in solvent or dispersion medium; then heat, thus manufacture the copper nitride particulate described in any one of above-mentioned [1] ~ [5].
The manufacture method of the copper nitride particulate [7] according to above-mentioned [6], wherein, copper source comprise be selected from inorganic mantoquita, organic copper salt and copper complex more than one.
The manufacture method of the copper nitride particulate [8] according to above-mentioned [6] or [7], wherein, nitrogenous source comprise be selected from ammonia or ammonium salt compound, urea, urea derivatives compound, nitrate compound, amine compound and triazo-compound more than one.
The manufacture method of the copper nitride particulate [9] according to any one in above-mentioned [6] ~ [8], wherein, copper source combines with nitrogenous source or coordination becomes nitrogenous copper complex together.
The manufacture method of the copper nitride particulate [10] according to any one in above-mentioned [6] ~ [9], it is characterized in that, protective material is the carboxyl with at least more than one, the compound of amino and/or hydroxyl.
The manufacture method of the copper nitride particulate [11] according to any one in above-mentioned [6] ~ [10], solvent to be boiling point the be organic solvent of more than 100 DEG C.
The manufacture method of the copper nitride particulate [12] according to any one in above-mentioned [6] ~ [11], Heating temperature is 100 ~ 250 DEG C.
The manufacture method of the copper nitride particulate [13] according to any one in above-mentioned [6] ~ [12], copper source relative to the concentration of solvent, to be converted into Cu
1+or Cu
2+concentration count 0.0001 ~ 1mol/L.
[14] a distribution ink material, comprises the copper nitride particulate described in above-mentioned [1].
[15] printing base, is coated with the distribution ink material described in above-mentioned [14].
[16] printing base, by heating the printing base described in above-mentioned [15], forming copper metal film by copper nitride particulate, thus obtaining.
According to the present invention, can provide and not there is the instability of metallic copper, the copper nitride particulate of the problem of pyroprocessing and its manufacture method in essence.This copper nitride particulate due to distribution can be carried out, have scale resistance for air and glassware for drinking water by printing, so, waited by printing on film, draw distribution, after the thermal treatment of less than 300 DEG C can be provided, present the material of electroconductibility.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the copper nitride particulate that embodiment 1 obtains, the XRD figure of Yi Jitong, cupric oxide and copper nitride.
Fig. 2 is the XRD spectra of the copper nitride particulate that embodiment 1,2,3 and 8 obtains.
Fig. 3 is the tem observation image of the copper nitride particulate that embodiment 1 obtains.
Fig. 4 is the tem observation image of the copper nitride particulate that embodiment 3 obtains.
Fig. 5 is the spectrogram of the differential thermal balance analysis (normal pressure and decompression) of the copper nitride particulate that embodiment 1 obtains.
Embodiment
Copper nitride particulate of the present invention, primary particle particle diameter is 1 ~ 100nm and decomposition temperature is less than 300 DEG C.
The primary particle size of copper nitride particulate of the present invention is 1 ~ 100nm, this means in electron microscope observation, the at least minor axis diameter of primary particle is 1 ~ 100nm, this is that decomposition temperature in order to reduce copper nitride particulate is necessary, its primary particle size is preferably below 50nm, be more preferably below 30nm, more preferably below 20nm, most preferably be below 10nm.
The particle diameter of offspring is preferably less than 1 μm, and such as, when making ink for inking, the coating of ink is good, and inkjet nozzle can not be made to pass through from inkjet nozzle with blocking.The form of offspring is preferably that to have be in fact spherical particle shape, and such as, when using as coating solution, mobility is excellent, and is suitable for tight filling after coating.Spherical, even if be not spherical passable completely yet, also can be aspect ratio be such as less than 3 degree, preferably less than 1.5 degree there are differences between major axis and minor axis like that.The particle shape of primary particle is, any particle shapes such as such as horn shape, needle-like, grain of rice shape, but preferably offspring easily becomes spherical shape.
Copper nitride particulate of the present invention, in differential thermal balance analysis (normal pressure), has the decomposition temperature that adjoint weight (quality) reduces in the scope of 70 DEG C ~ 300 DEG C.Decomposition temperature be less than 300 DEG C this can bring following advantage: using copper nitride particulate as distribution ink material, after being coated with using polymeric substrate or film as printing base, when carrying out heat treated, printing base can at the temperature that can not be subject to the damage that heat causes, such as, the temperature of melting and/or distortion, decomposition, carbonization processes under can not be subject to.
Copper nitride particulate of the present invention has following copper nitride (Cu
3n) crystal structure: in powder x-ray diffraction, has at least more than one the diffraction peak deriving from copper nitride in any one region of 21.5 ~ 24.5 ° under CuK α line and 31.0 ~ 34.0 °, 39.0 ~ 42.0 °, 46.0 ~ 49.0 °.
Copper nitride particulate described in the present invention, also can provide with the form of powder or colloidal dispersion, also can in order to give copper nitride particle dispersibility, stability and use suitable protective material.
Copper nitride particulate of the present invention, can pass through copper source and nitrogenous source, or copper source, nitrogenous source and protective material dissolves or is scattered in organic solvent or dispersion medium, and then heating obtains.
As the copper-containing compound becoming copper source, can exemplify out following as Inorganic Copper salt, organic copper salt or copper complex class, the Oxidation Number of the copper comprised in mantoquita or copper complex class is any state of monovalence or divalence.In addition, in order to make mantoquita or copper complex class stabilization, can be arbitrary number of 0 ~ 6 with the Molecules of copper coordination.
As Inorganic Copper salt, cupric chloride, cupric bromide, cupric iodate, cupric iodide, cupric fluoride, ventilation breather, cupric cyanide, copper azide, cupric ammonium chloride, copper hydroxide, Tubercuprose, COPPER OXYCHLORIDE 37,5, cupric perchlorate, cupric phosphate, Repone K copper, copper sulfate, Basic Chrome Sulphate, copper sulfate, cupric sulfide etc. can be exemplified out.In addition, also the oxide compounds such as cupric oxide can be utilized.
As organic copper salt, be carboxyl type, hydroxycarboxylic acid type, amino acid pattern, alcohol salt form etc.
Carboxyl type refers to, carbonatoms is straight-chain or the branch-like of 1 ~ 20, saturated or the aliphatic unsaturated hydrocarbon of ring-type and carboxyl are combined with copper and are formed, concrete can exemplify out venus crystals, propionic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid copper, cupric octoate, n-nonanoic acid copper, capric acid copper, undecanoic acid copper, dodecylic acid copper, tetradecanoic acid copper, hexadecanoic acid copper, margaric acid copper, octadecanoic acid copper, ethyl acetoacetic acid copper, trifluoroacetylacetone copper, vinylformic acid copper, propynoic acid copper, methacrylic acid copper, β-crotonic acid copper, iso-crotonic acid copper, cupric oleate, ricinolic acid copper, cupric benzoate, toluic acid copper, naphthoic acid copper, styracin copper etc.In addition, can also exemplify out carbonatoms be 1 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon in conjunction with the polycarboxy type of two or more carboxyl.Such as, fumaric acid copper, toxilic acid copper, phthalic acid copper, m-phthalic acid copper, terephthalic acid copper, cupric oxalate, propanedioic acid copper, succsinic acid copper, pentanedioic acid copper, hexanodioic acid copper, pimelic acid copper, suberic acid copper, nonane diacid copper, sebacic acid copper etc. can be exemplified out.
In addition, as hydroxycarboxylic acid type, the molecule be combined with copper to be carbonatoms be 1 ~ 20 straight-chain or branch-like, saturated or the aliphatic unsaturated hydrocarbon of ring-type has the molecule of more than one carboxyl and more than one hydroxyl, such as, hydroxyethanoic acid copper can be exemplified out, cupric lactate, oxomalonic acid copper, R-Glyceric acid copper, hydroxybutyric acid copper, 2-hydroxybutyric acid copper, 3-hydroxybutyrate copper, gamma-hydroxybutyric acid copper, oxysuccinic acid copper, cupric tartrate, citromalic acid copper, Cuprocitrol, isocitric acid copper, leucine copper, mevalonic acid copper, pantoic acid copper, ricinolic acid copper, ricinelaidic acid copper, pentacosamic acid copper, quininic acid copper, copper gluconate etc.
In addition, as amino acid pattern, the molecule be combined with copper to be carbonatoms be 1 ~ 20 straight-chain or branch-like, saturated or the aliphatic unsaturated hydrocarbon of ring-type has the molecule of more than one carboxyl and more than one amino, such as, L-Ala mantoquita can be exemplified out, arginine mantoquita, l-asparagine mantoquita, aspartic acid copper, halfcystine mantoquita, glutamine mantoquita, cupric glutamate, glycine mantoquita, Copper histidine, Isoleucine mantoquita, leucine mantoquita, Methionin mantoquita, methionine(Met) mantoquita, phenylalanine mantoquita, proline(Pro) mantoquita, Serine mantoquita, copper-threonine, tryptophane mantoquita, tyrosine mantoquita, α-amino-isovaleric acid mantoquita etc.
In addition, as alcohol salt form, to be carbonatoms be 1 ~ 20 straight-chain or branch-like, ring-type the molecule that is combined with copper by Sauerstoffatom of saturated or aliphatic unsaturated hydrocarbon, methoxyl group copper, oxyethyl group copper, propoxy-copper etc. can be exemplified out.
In addition, as other organocopper compound, the cyclooctadiene mixture, benzene sulfinic acid hydrate, cupric dimethyldithiocarbamate, Tetrafluoroboric acid copper, copper trifluoromethanesulfcomposite, tetrachloro copper acid potassium etc. of Perfluoroacetone copper, hexafluoro-2,4-diacetylmethane copper (I) can be exemplified out.
In order to form copper complex, as the molecule of copper-containing compound being coordinated in above-mentioned Inorganic Copper salt and organic copper salt, mineral ligand and organic ligand can be roughly divided into, as mineral ligand, water outlet, ammonia, carbon monoxide etc. can be exemplified.In addition, as organic ligand, refer to comprise more than one, can with carbonatoms be 1 ~ 40 straight-chain or branch-like, the saturated or Sauerstoffatom of aliphatic unsaturated hydrocarbon coordination of ring-type and/or the molecule of nitrogen-atoms, but, except these parts, as long as copper-containing compound stabilization can be made, be then not particularly limited.
As particularly preferred copper-containing compound, the molecule that has and to decompose below 250 DEG C after preparing copper nitride particulate, by heat treated or volatilize or the ion compound as negatively charged ion can be exemplified out, as cupric chloride, cupric bromide, copper sulfate, cupric nitrate, Tubercuprose, venus crystals, propionic acid copper, copper butyrate, valeric acid copper, caproic acid copper, enanthic acid copper, cupric octoate, n-nonanoic acid copper, capric acid copper, undecanoic acid copper, dodecylic acid copper etc.
As nitrogenous source, more than one the compound comprising and selecting from ammonia or ammonium salt compound, urea, urea derivatives compound, nitrate compound, amine compound and trinitride can be exemplified out.
As ammonium salt compound, ammonium azide, ammonium benzoate, ammonium chloride, electric salt (SALAMMONIAC), ammonium chlorate, ammoniumper chlorate, ammonium permanganate, ammonium chromate, ammonium acetate, ammonium nitrate, ammonium hydroxide, volatile salt, bicarbonate of ammonia, ammonium mercaptoacetate, ammonium thiocyanate, ammonium bifluoride, ammonium iodide, ammonium iodate, ammonium sulfate, ammonium phosphate etc. can be exemplified out.In addition, urea derivatives to be more than one amino in urea with carbonatoms be 1 ~ 20 straight-chain or the compound that combines of branch-like, the saturated or aliphatic unsaturated hydrocarbon of ring-type, aromatic nucleus, benzylurea, N-ethyl-N'-phenylurea, O-ethoxyl urea, m-oxethyl phenylurea, dulcin, N can be exemplified out, N '-diphenyl urea, N, N '-sym-diphenylurea, tetraphenyl urea, N-benzoyl urea etc.
In addition, amine compound refer to carbonatoms be 1 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon in conjunction with the molecule of the amino of 1 grade ~ 4 grades, can to exemplify out such as, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, hexahydroaniline, 2-methyl cyclohexylamine, allylamine, oleyl amine, aniline, Tolylamine, ethylbenzene amine etc.In addition, the polyhydric amine compounds of the amino with more than 21 grade ~ 4 grades can also be exemplified in molecule, as diamines, diaminobutane can be enumerated by concrete example, hexamethylene-diamine, trimethylhexamethylenediamine, m-xylene Methionin diamines, Ursol D, mphenylenediamine, toluylene diamine, 4,4'-diaminodiphenyl-methane, 4,4'-diamino-diphenyl ether, 3,4'-diamino-diphenyl ether, 4,4'-benzidine, 3,3'-dimethyl 4,4'-benzidine, 4,4'-diaminodiphenyl sulfide, 2,6-diaminonaphthalene, 4,4'-bis-(p-aminophenyl oxygen base) sulfobenzide, two (the m-aminophenyl oxygen base) sulfobenzide of 4,4'-, two (the p-aminophenyl oxygen base) benzophenone of 4,4'-, two (the m-aminophenyl oxygen base) benzophenone of 4,4'-, two (p-aminophenyl sulfydryl) benzophenone of 4,4'-, two (p-aminophenyl sulfydryl) sulfobenzides of 4,4'-etc., as triamine, "-triaminotriphenyl the methylmethane that can exemplify out 4,4' particularly, 4, triamterene etc.In addition, polyhydric amine compounds can be roughly divided into the aromatic polyamines such as aliphatic polyamine and Ursol D such as hexamethylene-diamine.
As trinitride, azoimide, sodiumazide etc. can be exemplified out.Copper source and nitrogenous source also can use the nitrogenous copper complex of combination or coordination.
As preferred nitrogenous compound, can exemplify out and be decomposed below 250 DEG C by heating when preparing copper nitride particulate or volatilize, ammonia, ammonium chloride, brometo de amonio, ammonium acetate, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine.Particularly preferably be, have as ammonium salts such as the ammonia of ammonia of gaseous volatilization after reaction and ammonium chloride, brometo de amonio, ammonium acetates.
As mentioned above, copper nitride particulate of the present invention to be dissolved or be scattered in solvent or dispersion medium by copper source and nitrogenous source or copper source, nitrogenous source and protective material, then heating obtain.
As solvent, as long as do not hinder the dispersion of particulate, boiling point is more than 100 DEG C, preferred boiling point 200 DEG C, then be not particularly limited, preferably with an organic solvent, alkylol cpd, ether compound, amine compound, polyhydric amine compounds, amino alcohol compound, amide compound, hydrocarbon compound etc. can be exemplified out.
As alkylol cpd, to be carbonatoms be 5 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon on combine the compound of a hydroxyl, concrete can exemplify out amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, crotyl alcohol, 3-butene-1-ol, 4-amylene-1-ol, 5-hexen-1-ol, 6-heptene-1-alcohol, 7-octen-1-ol, 8-nonylene-1-ol, hexalin, hexahydrobenzyl alcohol, 4 methyl cyclohexanol, phenol, cresols, 4-ethylphenol.In addition, also can exemplify out carbonatoms be 2 ~ 10 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon combine the polyol compound of more than 2 hydroxyls, as ethylene glycol, 1, ammediol, 1,2-propylene glycol, BDO, 1,3-PD, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-butylene-Isosorbide-5-Nitrae-glycol etc.
In addition, as ether compound, to be carbonatoms be 2 ~ 10 straight chain or branch-like, ring-type saturated or unsaturated hydrocarbons interchain be cross-linked more than 1 by the oxygen element of more than 1.And because ether compound boiling point is low, during in order to obtain synthesizing, the boiling point of necessity, also can make on hydrocarbon chain in conjunction with more than one hydroxyl.Concrete can exemplify out, glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether etc.
In addition, as amine compound, to be carbonatoms be 5 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon on combine the compound of the amino of 1 grade ~ 4 one-levels in charge of a grade.Amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, hexahydroaniline, 2-methyl cyclohexylamine, allylamine, oleyl amine, aniline, Tolylamine, ethylbenzene amine etc. can be exemplified out.In addition, as carbonatoms be 2 ~ 10 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon on combine the polyhydric amine compounds of the amino of more than 21 grade ~ 4 one-levels in charge of a grade, quadrol, 1 can be exemplified out, 3-diaminopropanes, 1,4-diamino-2-methylpropane, 1,4-Diaminobutane, 1,5-1,5-DAP, hexamethylene-diamine, 1,7-diaminoheptane, 1,8-diamino-octane etc.
In addition, as amino alcohol compound, can exemplify out carbonatoms be 5 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon R on combine the hydroxyl of more than 1 and more than 1 amino compound.
As amide compound, can exemplify out carbonatoms be 2 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon R on combine the compound of 1 carboxylic acid amide, the nitrogen of carboxylic acid amide is arbitrary level in 1 grade or 2 grades, 3 grades.
As dispersion medium, above-mentioned solvent can be used, even if not dissolved copper source and nitrogenous source, or copper source, nitrogenous source and protective material, when working as dispersion agent, also by the heating for the preparation of copper nitride particulate, can become and work as solvent.
As the protective material used in the present invention, alkylol cpd, polyol compound, amine compound, polyhydric amine compounds, carboxylic acid cpd, polycarboxylic compounds, macromolecular compound etc. can be exemplified out.In addition, these are except playing other purposes as protective material, solvent self also can be made as protective material, also can utilize the molecule that can be combined with above-mentioned copper-containing compound and nitrogenous compound.
The alkylol cpd used as protective material or polyol compound, ether compound, amine compound, polyhydric amine compounds, amino alcohol compound, amide compound, hydrocarbon compound, can use in above-claimed cpd more than one.
As carboxylic acid cpd, to be carbonatoms be 2 ~ 20 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon R on combine the compound of 1 carboxyl, represent with the chemical structural formula of R-COOH.
As polycarboxylic compounds, to be carbonatoms be 2 ~ 10 straight-chain or branch-like, ring-type saturated or aliphatic unsaturated hydrocarbon R in conjunction with the compound of the carboxyl of more than 2, with R (-COOH)
nchemical structural formula represent that there is the value of n=2 ~ 8.
As macromolecular compound, having molecular weight is 1,000 ~ 100, and the molecular weight of 000 can exemplify out polyvinylpyrrolidone class, polyvinyl alcohol, polyethylene glycols, polyoxyalkylene class, acrylicacidandesters class, methacrylic acid and ester class thereof.
As protective material, the alkylol cpd of preferably less than 250 DEG C decomposition or volatilization, polyol compound, amine compound, polyhydric amine compounds, carboxylic acid cpd, polycarboxylic compounds, macromolecular compound.
React the temperature of carrying out in the present invention and be preferably 100 DEG C ~ 250 DEG C, preferred, the temperature range of 150 DEG C ~ 200 DEG C can be exemplified out.If temperature is low, copper raw material does not dissolve, and reaction is not carried out.In addition, the upper limit of temperature of reaction is limited by the boiling point of solvent, and when temperature is too high, copper nitride decomposition becomes copper or cupric oxide.Reactive system can select any one in decompression, normal pressure, pressurization as required.As reaction system, if normal pressure, can simplification device and operation, so preferably.
There is no particular limitation for heating means, but by the homogeneity of heated solution internal temperature, can utilize the electromagnetic wave heatings such as microwave to realize.
In the manufacture method of copper nitride particulate of the present invention, copper-containing compound affects production efficiency and the particle diameter of particulate relative to the concentration of organic solvent.If the concentration of copper-containing compound is too low, the concentration due to the particulate be obtained by reacting is low so productivity reduces.In addition, if the excessive concentration of copper-containing compound, the particle diameter obtaining particle just becomes excessive.Therefore, in the manufacture method of copper nitride particulate, the concentration of copper-containing compound, with Cu
1+or Cu
2+densitometer be preferably the concentration of 0.0001 ~ 1mol/L, more preferably 0.001 ~ 0.1mol/L.
In the manufacture method of copper nitride particulate, when using ammonia, in reaction, nitrogenous source is supplied in reaction system by unlimited, but when using solid or liquid nitrogenous source, the feed rate of nitrogen becomes limited.As the amount of nitrogenous compound that nitrogenous source adds, be preferably 0.01 ~ 100 equivalent relative to copper concentration, if due to the amount of nitrogenous source few, then can there is unreacted cupric ion, yield reduces, so be more preferably 0.4 ~ 100 equivalent.
In the manufacture method of copper nitride particulate, adding protectant amount, is 0.01 ~ 100 equivalent relative to copper concentration, is more preferably 0.1 ~ 10 equivalent.
Copper nitride particulate of the present invention, as mentioned above, in differential thermal balance analysis (normal pressure), has the decomposition temperature that adjoint weight (quality) reduces in the scope of 70 DEG C ~ 300 DEG C.This copper nitride particulate, owing to being carried out distribution, be had scale resistance for air and glassware for drinking water by printing, so can provide, is drawn distribution by printing etc., is presented the material of electroconductibility after the thermal treatment of less than 300 DEG C on film.Namely, following advantage can be brought: using copper nitride particulate as distribution ink material, after being coated with using polymeric substrate or film as printing base, when carrying out heat treated, printing base can not be subject to damage that heat causes such as, processes under can not being subject to the temperature of melting and/or distortion, decomposition, carbonization.
As mentioned above, according to the present invention, can providing package containing copper nitride particulate of the present invention distribution ink material, be coated with this distribution ink material printing base and by by this printing base in less than 300 DEG C thermal treatments, the printing base being formed copper metal film by copper nitride particulate.By distribution ink material to the coating on printing base, use ink jet method, spraying method, electrostatic spraying, web plate method, silk screen print method etc., can be undertaken by well-established law.The copper metal film obtained after thermal treatment, demonstrates electroconductibility, but by turning to below 50nm by fine for the primary particle size of the copper nitride particulate of use, being preferably below 30nm, being more preferably below 20nm, most preferably below 10nm, can obtaining as 10
-5the practical electroconductibility of Ω.
Embodiment
Below, by embodiment, the present invention is specifically described, but the present invention is not limited to these embodiments.
Embodiment 1
The 1-octanol solution (50mL) of venus crystals (II) (0.5mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, be 190 DEG C of heating 1 hour with solution temperature, confirm red-purple throw out.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.Powder x-ray diffraction device (M21X:40kV, 200mA, CuK α of マ ッ Network サ イ エ Application ス company) is utilized to carry out crystallizing layer analysis (XRD determining) to this powder, and carry out transmission electron microscope (TEM) observation (the TECNAI G2 of FEI Co., acceleration voltage is 200kV, and transmitter current is 8 μ A).
The particle diameter of the primary particle of the copper nitride particulate obtained is 10 ~ 50nm, and the particle diameter of offspring is 0.1 ~ 0.2 μm.For primary particle and offspring, carry out image analysis as follows.
The judgement of primary particle is by the contrast analysis (DigitalMicrograph) to tem observation image and undertaken by the judgement merging carried out the visual of original image.The identification of the primary particle undertaken by contrast analysis, be part within 300 by extracting contrast difference, region judges crystal interface by original image together therewith, using the particle diameter of this minor axis diameter as primary particle.
The judgement of offspring is carried out by the contrast analysis of tem observation image with by the visual judgement merging of original image.Analyzed by contrast, extracting contrast difference is region within 1100, combines therewith, by visual identification particle interface each other.Using the particle diameter of the major diameter of the offspring through a series of process gained as offspring.
Thermolysis mensuration employing differential thermal balance (the Thermo plus EVO II of (strain) リ ガ Network: heat-up rate is 5 DEG C/min, aluminum oxide standard model, in Ar air-flow, normal pressure or decompression (600Pa)) measure.
Fig. 1 represents the XRD spectra of the copper nitride particulate obtained in embodiment 1, the XRD figure shape of Yi Jitong, cupric oxide and copper nitride.Fig. 3 represents the tem observation image of the copper nitride particulate obtained in embodiment 1.Fig. 5 represents the result of the differential thermal balance analysis (normal pressure and decompression) of the copper nitride particulate obtained in embodiment 1.Namely, according to differential thermal balance analysis (normal pressure), have below 225 DEG C and reduce heat decomposition temperature together with weight.
Embodiment 2
The 1 nonyl alcohol solution (50mL) of venus crystals (II) (0.5mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, be 190 DEG C of heating 1 hour with solution temperature, confirm red-purple throw out.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The particle diameter of the primary particle of the copper nitride particulate obtained is 10 ~ 20nm, and the particle diameter of offspring is 0.1 ~ 0.2 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 220 DEG C.
Fig. 2 represents the XRD spectra of the copper nitride particulate obtained in example 2.
Embodiment 3
The 1-octanol solution (20mL) of cupric octoate (II) (0.28mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, with 190 DEG C of heating 1 hour, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The minor axis diameter of the primary particle of the copper nitride particulate obtained is 1 ~ 5nm, and major diameter is 50 ~ 100nm, and the particle diameter of offspring is 0.1 ~ 0.5 μm.According to differential thermal balance analysis (normal pressure), below near 220 DEG C, the phenomenon that the weight that the thermolysis that the copper nitride particulate obtained has the sad and copper nitride existed with surface is accompanied reduces.
Fig. 2 represents the XRD spectra of copper nitride particulate obtained in embodiment 3.Fig. 4 represents the tem observation image of copper nitride particulate obtained in embodiment 3.
Embodiment 4
The 1-octanol solution (20mL) of cupric octoate (II) (0.28mmol) and nonyl amine (1mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, with 190 DEG C of heating 1 hour, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The particle diameter of the primary particle of the copper nitride particulate obtained is 20 ~ 30nm, and the particle diameter of offspring is 0.2 ~ 0.5 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 250 DEG C.
Embodiment 5
The 1-octanol solution (20mL) of tetradecanoic acid copper (II) (0.28mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, with 190 DEG C of heating 1 hour, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The copper nitride particulate obtained is that the minor axis diameter of primary particle is 5 ~ 10nm, major diameter is the needle-like crystal of 50 ~ 100nm, and the particle diameter of offspring is 0.1 ~ 0.2 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 250 DEG C.
Embodiment 6
The 1-octanol solution (20mL) of lauric acid copper (II) (0.28mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, with 190 DEG C of heating 1 hour, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The copper nitride particulate obtained is that the minor axis diameter of primary particle is 5 ~ 10nm, major diameter is the needle-like crystal of 50 ~ 100nm, and the particle diameter of offspring is 0.1 ~ 0.15 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 300 DEG C.
Embodiment 7
The dodecane solution (20mL) of cupric octoate (II) (0.28mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 230 DEG C, heat 1 hour with when 190 DEG C, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The particle diameter of the primary particle of the copper nitride particulate obtained is 10 ~ 50nm, and the particle diameter of offspring is 0.1 ~ 0.3 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 240 DEG C.
Embodiment 8
The 1-octanol solution (10mL) of nitrine ammonia copper (II) (0.1mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 220 DEG C, heat 1 hour with when 180 DEG C, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The particle diameter of the primary particle of the copper nitride particulate obtained is 50 ~ 100nm, and the particle diameter of offspring is 0.1 ~ 0.5 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 221 DEG C.
Fig. 2 represents the XRD spectra of the copper nitride particulate obtained in embodiment 8.
Embodiment 9
The 1-octanol solution (10mL) of nitrine ammonia copper (II) (0.2mmol) and hexylamine (1mmol) has been prepared in three-necked flask.While be blown into ammonia, adopt the oil bath of 220 DEG C, with 180 DEG C of heating 1 hour, confirm black precipitate.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The particle diameter of the primary particle of the copper nitride particulate obtained is 50 ~ 100nm, and the particle diameter of offspring is 0.2 ~ 0.5 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 250 DEG C.
Embodiment 10
The 1 nonyl alcohol solution (50mL) of venus crystals (II) (0.5mmol) and ammonium acetate (5mmol) has been prepared in three-necked flask.While be blown into nitrogen, adopt the oil bath of 230 DEG C, be 190 DEG C of heating 1 hour with solution temperature, confirm red-purple throw out.This throw out is filtered by centrifugation, after repeatedly cleaning with normal hexane, has carried out vacuum-drying.XRD determining and tem observation have been carried out to this powder.
The particle diameter of the primary particle of the copper nitride particulate obtained is 10 ~ 50nm, and the particle diameter of offspring is 0.1 ~ 0.5 μm.According to differential thermal balance analysis (normal pressure), the copper nitride particulate obtained has the heat decomposition temperature reducing with weight and accompany below 250 DEG C.
The combination of the synthesis condition of embodiment and copper source, nitrogenous source, protective material, solvent and the sedimentary XRD analysis result obtained are shown in table 1.
Table 1
Industry utilizes possibility
The invention provides the copper nitride that decomposition temperature is less than 300 DEG C, and the material that can be provided metallic copper by the heating below 300 DEG C is provided.The distribution ink material for such as printed electronic device can be expected.
Claims (16)
1. a copper nitride particulate, the particle diameter of primary particle is 1 ~ 100nm, and decomposition temperature is less than 300 DEG C.
2. copper nitride particulate according to claim 1, the particle diameter of offspring is less than 1 μm.
3. copper nitride particulate according to claim 1 and 2, in differential thermal balance is analyzed, has the decomposition temperature of adjoint weight minimizing the scopes of 70 DEG C ~ 300 DEG C.
4., according to the copper nitride particulate in claims 1 to 3 described in any one, in electron microscope observation, secondary particle is spherical.
5. according to the copper nitride particulate in Claims 1 to 4 described in any one, in powder x-ray diffraction, in any one region of 21.5 ~ 24.5 ° under CuK α line, 31.0 ~ 34.0 °, 39.0 ~ 42.0 ° and 46.0 ~ 49.0 °, there is the diffraction peak that at least more than one derives from copper nitride.
6. a manufacture method for copper nitride particulate, is characterized in that, will
Copper source and nitrogenous source, or
Copper source, nitrogenous source and protective material
Dissolve or be scattered in solvent or dispersion medium, then heating, thus the copper nitride particulate described in any one of manufacturing claims 1 ~ 5.
7. the manufacture method of copper nitride particulate according to claim 6, wherein, copper source comprise be selected from inorganic mantoquita, organic copper salt and copper complex more than one.
8. the manufacture method of the copper nitride particulate according to claim 6 or 7, wherein, nitrogenous source comprise be selected from ammonia or ammonium salt compound, urea, urea derivatives compound, nitrate compound, amine compound and triazo-compound more than one.
9. according to the manufacture method of the copper nitride particulate in claim 6 ~ 8 described in any one, wherein, copper source becomes nitrogenous copper complex with nitrogenous source combination or coordination together.
10. according to the manufacture method of the copper nitride particulate in claim 6 ~ 9 described in any one, it is characterized in that, protective material is the compound with more than one carboxyl, amino and/or hydroxyl.
11. according to the manufacture method of the copper nitride particulate in claim 6 ~ 10 described in any one, solvent to be boiling point the be organic solvent of more than 100 DEG C.
12. according to the manufacture method of the copper nitride particulate in claim 6 ~ 11 described in any one, and Heating temperature is 100 ~ 250 DEG C.
13. according to the manufacture method of the copper nitride particulate in claim 6 ~ 11 described in any one, copper source relative to the concentration of solvent, to be converted into Cu
1+or Cu
2+concentration count 0.0001 ~ 1mol/L.
14. 1 kinds of distribution ink materials, comprise copper nitride particulate according to claim 1.
15. 1 kinds of printing bases, are coated with distribution ink material according to claim 14.
16. 1 kinds of printing bases, by heating printing base according to claim 15, forming copper metal film by copper nitride particulate, thus obtaining.
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| JP2013225296A JP6057379B2 (en) | 2013-01-31 | 2013-10-30 | Copper nitride fine particles and method for producing the same |
| PCT/JP2014/052321 WO2014119748A1 (en) | 2013-01-31 | 2014-01-31 | Fine copper nitride particles and production method therefor |
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| WO2015147561A1 (en) * | 2014-03-26 | 2015-10-01 | 전자부품연구원 | Composite material with which conductor pattern can easily be formed, method for manufacturing the composite material, copper nitride seed material of the composite material and method for synthesising the copper nitride |
| JP6574553B2 (en) * | 2014-06-26 | 2019-09-11 | 昭和電工株式会社 | Conductive pattern forming composition and conductive pattern forming method |
| RU2647056C1 (en) * | 2017-07-11 | 2018-03-13 | Юлия Алексеевна Щепочкина | Steel |
| RU2647055C1 (en) * | 2017-07-11 | 2018-03-13 | Юлия Алексеевна Щепочкина | Steel |
| KR102303767B1 (en) * | 2017-11-01 | 2021-09-23 | 한국전자기술연구원 | Method for manufacturing copper nitride powder for conductor pattern |
| CN111450867A (en) * | 2020-05-09 | 2020-07-28 | 青岛科技大学 | Cu for electrocatalytic carbon dioxide reduction3Preparation method of N nano catalyst |
| CN115057417B (en) * | 2022-06-08 | 2023-09-12 | 安徽大学 | Preparation of copper nitride nano-sheet and application of copper nitride nano-sheet in formate electrosynthesis |
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| US20070187812A1 (en) * | 2004-06-07 | 2007-08-16 | Akira Izumi | Method for processing copper surface, method for forming copper pattern wiring and semiconductor device manufactured using such method |
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| JP5778382B2 (en) * | 2008-10-22 | 2015-09-16 | 東ソー株式会社 | Composition for producing metal film, method for producing metal film, and method for producing metal powder |
| JP5243510B2 (en) * | 2010-10-01 | 2013-07-24 | 富士フイルム株式会社 | Wiring material, wiring manufacturing method, and nanoparticle dispersion |
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| JONGLAK CHOI ET AL: ""Solvothermal Synthesis of Nanocrystalline Copper Nitride from an Energetically Unstable Copper Azide Precursor"", 《INORG. CHEM》 * |
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| CN110642304A (en) * | 2019-10-09 | 2020-01-03 | 上海师范大学 | Trimetal nitride material for super capacitor and preparation method thereof |
| CN110642304B (en) * | 2019-10-09 | 2021-12-31 | 上海师范大学 | Trimetal nitride material for super capacitor and preparation method thereof |
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