CN101130860A - Material for forming film and method for producing film - Google Patents
Material for forming film and method for producing film Download PDFInfo
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- CN101130860A CN101130860A CNA2007101417110A CN200710141711A CN101130860A CN 101130860 A CN101130860 A CN 101130860A CN A2007101417110 A CNA2007101417110 A CN A2007101417110A CN 200710141711 A CN200710141711 A CN 200710141711A CN 101130860 A CN101130860 A CN 101130860A
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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
- C23C16/22—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
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
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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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
Abstract
The present invention provides a raw material which is suitable for making the thin film containing the zinc and a method for making the thin film using the chemical gas phase deposit method of the raw material. The film forming raw material is formed by the solution which is dissolved by 0.1 to 1 mol bis (pentane-2, 4-diketo) zinc anhydrate as the essential component relative to the organic solvent which does not contain hydroxyl, and the steam which is got by gasifying the film forming used raw material and contains bis (pentane-2, 4-diketo) zinc anhydrate is leaded to the substrate, and the steam is decomposed and/or chemically reacted to form a thin film containing zinc atom on the substrate.
Description
Technical field
The present invention relates to contain the film formation raw material of zinc, in more detail, relating to the film that forms by there are two (pentane-2,4-diketo) zinc that 0.1～1 mole of conduct must composition not have the solution of hydrate with respect to the 1000ml organic solvent dissolution forms with raw material and has used this film to form the manufacture method of the film of usefulness raw material.
Background technology
The film that contains zinc has various characteristicses such as optical characteristics, electrical characteristic, catalytic activity, as the member of electronic unit or optics.
Manufacture method as above-mentioned film, can list MOD method, chemical Vapor deposition processs etc. such as flame deposited method, sputtering method, ion plating method, coated heat decomposition method or sol-gel method, owing to have and form controlled and the step coverage excellence, be fit to mass production, can mix many advantages such as integrated, therefore comprise the manufacture method that chemical vapour deposition (below, only the be called CVD sometimes) method of ALD (Atomic Layer Deposition ald) method is best suited for.
In the CVD method, consider from stability and security aspect as precursor, study the beta-diketon complex compound usually.For example, the CVD method that is easy to promptly two (pentane-2, the 4-diketo) zinc of evaporable solid precursor of using is disclosed in patent documentation 1～3.Disclosed two (pentane-2,4-diketo) zinc comprise hydrate and non-hydrate (no hydrate) in patent documentation 3, in the making of film, consider from the angle of crystallinity and reproducibility, are preferably 1 hydrate.In addition, in patent documentation 4, disclosing to be the technology of the solution of solvent as the CVD raw material with hydrocarbon or alcohol.As hydrocarbon solvent, illustration hexane, heptane, octane, nonane, decane, pentamethylene, hexanaphthene, suberane, cyclooctane, cyclononane; As alcohols, illustration methyl alcohol, ethanol, propyl alcohol, butanols; As precursor, illustration two (pentane-2,4-diketo) zinc, still, do not have concrete record about two (pentane-2,4-diketo) zinc solution.In non-patent literature 1, the CVD method of the diethylene glycol monomethyl ether solution of two (pentane-2, the 4-diketo) zinc of general as raw material disclosed.In addition, in patent documentation 5, disclosing at 25 ℃ is down promptly two (octane-2, the 4-diketo) zinc of two (beta-diketon base) zinc, two (2,2-dimethyl-6-ethyl decane-3,5-diketo) zinc of liquid.
Two (pentanes-2, the 4-diketo) to be fusing point be about 130 ℃, be dystectic solid about 137 ℃ with the form of 1 hydrate with the form of no hydrate zinc, in the necessary technology of gasification process such as CVD, if utilize the volatilization that causes owing to distillation, then in the volatile quantity deficiency, volatile quantity through the time unstripped gas such as variation supply with on the property and have problems.Utilize in the technology of solution in solution C VD etc. or MOD method etc., the problem of existence is, is being fit to can not get not existing in solution materials under the concentration of using the solution of solid phase.As the aliphatic hydrocarbon kind solvent, can not give sufficient solvability sometimes, for pure series solvent, because two (pentane-2,4-diketo) zinc and pure hydroxyl reaction have the rotten problem of precursor.Two (beta-diketon base) zinc of patent documentation 5 disclosed liquid can be avoided these problems because solvability is also abundant, but differ satisfied surely for the volatility of precursor self.
Patent documentation 1: special fair 6-64738 communique (particularly claim 9)
Patent documentation 2: the spy opens 2003-236376 communique (particularly embodiment)
Patent documentation 3: the spy opens 2003-31846 communique (particularly paragraph 0015,0016)
Patent documentation 4: the spy opens 2005-298874 communique (particularly claim 1, paragraph 0012)
Patent documentation 5: the spy opens 2005-350423 communique (particularly claim 1～claim 6)
Non-patent literature 1:NREL/SR-520-3179December 2001 (particularly page 3)
Summary of the invention
The purpose of this invention is to provide the manufacture method that a kind of suitable manufacturing contains the film of the raw material of film of zinc and the chemical Vapor deposition process by having used this raw material.
The inventor etc. have carried out repeatedly research, found that to have used specific organic solvent not have the solution of hydrate as two (pentane-2,4-diketo) zinc of solvent, and under high density performance satisfactory stability, thus finished the present invention.
Promptly, the present invention is by providing two (pentanes-2 that 0.1～1 mole the necessary composition of conduct is arranged by the organic solvent dissolution that does not have hydroxyl with respect to 1000ml, the 4-diketo) zinc does not have the solution of hydrate and the film that forms forms and uses raw material, thereby has reached above-mentioned purpose.
In addition, the present invention achieves the above object by a kind of film-forming method is provided, described manufacture method is to import to contain on matrix above-mentioned film is formed the two (pentanes-2 that obtain with material gasification, the 4-diketo) zinc does not have the steam of hydrate, by making its decomposition and/or chemical reaction takes place, thereby on matrix, form the film that contains zinc atom.
Film of the present invention forms uses raw material, owing to show satisfactory stability under high density, can realize productivity good film manufacturing process.In addition, because volatility is good, it is useful following the raw material in the technology of gasification as CVD etc. especially.And, form the film that makes with raw material by film of the present invention and have various characteristicses such as optical characteristics, electrical characteristic, catalytic activity, can be as the member of electronic unit or optics.
Description of drawings
Fig. 1 represents that two (pentane-2,4-diketo) zinc do not have the IR figure of hydrate.
Fig. 2 represents the IR figure of two (pentane-2,4-diketo) zinc of commercially available product.
Fig. 3 represents that two (pentane-2,4-diketo) zinc do not have the result that hydrate and TG-DTA as the constituent of the diethylene glycol monomethyl ether of the organic solvent with hydroxyl measure.
The sketch chart of an example of employed CVD device in Fig. 4 the represents film-forming method that use in an embodiment, of the present invention.
Embodiment
It is that two (pentane-2,4-diketo) zinc is not had the precursor of hydrate as film that film of the present invention forms with raw material, with it as must composition being dissolved in the organic solvent with hydroxyl and the material that obtains.It is characterized in that, because the zinc precursor dissolve with abundant amount, therefore can realize productivity good film manufacturing process, and because volatility is good, the raw material in the special technology of following gasification as CVD etc. is useful.
Usually, two (pentane-2, the 4-diketo) zinc that can buy from market have the mixture of hydrate or hydrate and no hydrate.As hydrate, known have 1 hydrate.Having or not of water of hydration can be confirmed by the absorption that IR analyzes water of hydration.When two (pentane-2, the 4-diketo) attempted such when zinc is dissolved in the various organic solvents, suspension liquid or dissolved residue can occur.It is difficult removing suspension liquid or dissolved residue fully, can not be obtained the solution that does not have solid phase to exist under sufficient concentration by two (pentane-2, the 4-diketo) zinc that contain hydrate.
In addition,, have no particular limits, can use known general method for not having the manufacture method of hydrate as two (pentane-2,4-diketo) zinc that must composition of the present invention.For example can list: getting rid of under the non-water system environment of water, make zinc halide (zinc fluoride, zinc chloride, zinc bromide, zinc iodide), zinc sulfate, inorganic zinc salts such as zinc nitrate in the presence of alkali with pentane-2, the method of 4-two reactive ketones, under non-water system environment, make inorganic zinc salt and pentane-2,4-diketo sodium, pentane-2,4-diketo potassium, pentane-2, the method of alkali metal complexs such as 4-diketo lithium reaction, under non-water system environment, make dimethoxy zinc, alkoxide and pentanes-2 such as diethoxy zinc, the method of 4-two reactive ketones, under non-water system environment, make two (ethylamino) zinc, the amide and the pentane-2 of zinc such as two (propyl group amino) zinc, the methods of 4-two reactive ketones etc. are directly made the method for no hydrate; Will be with hydrate and the pentane-2 of water as solvent, inorganic zinc or inorganic zinc, the method that the water of hydration in two (pentane-2,4-diketo) zinc hydrates such as the alkalescence that the 4-diketone obtains reacting in the presence of the alkali such as sodium hydroxide etc. removes out.As the method for removing water of hydration, can list: the method for using the method for dewatering agent, dewatering by heating and decompression, the method for the two or more combinations of these methods.Obtain not having under the situation of hydrate from hydrate, removing water of hydration, in order to obtain film formation raw material as transparent, stable solution, two (the pentanes-2 that contain as impurity, the 4-diketo) the zinc hydrate converts by 1 hydrate and is preferably 1 mole below the %, more preferably 0.3 mole below the %.
Usually, in thin film fabrication technology, under the situation that the solution that will be dissolved with solid precursor uses as film precursor, solid precursor has sufficient solvability in solvent be necessary.If solvability is low, then can not obtain sufficient film forming speed, and can not obtain solubility limit (solution margin), therefore pass through the dilution of change in concentration or part organic solvent etc., solid is separated out and is become easily, will take place film forming speed through the time change, membranous deterioration.
Therefore, film of the present invention forms with in the raw material, as above-mentioned solvent, use the organic solvent that does not have hydroxyl, with respect to this organic solvent of 1000ml, two (pentanes-2, the 4-diketo) the zinc concentration of not having a hydrate is set at 0.1～1 mole, is preferably 0.2～1 mole.When two (pentane-2,4-diketo) zinc does not have hydrate and is lower than 0.1 mole, can not obtain sufficient productivity, when more than 1 mole,, solid might occur and separate out owing to diminish from the solubility limit of upper solubility limit.
Form with the organic solvent that does not have hydroxyl that can obtain above-mentioned concentration used in the raw material as film of the present invention, can list: ketone compounds, ether compound, ester compound, aromatic series compounds or have the hydrocarbon compound of cyano group.Described organic solvent can use separately, also can mix use more than 2 kinds.
As above-mentioned ketone compounds, can list: acetone, methyl ethyl ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), ethyl butyl ketone, butyrone, diisobutyl ketone, Methyl amyl ketone, pimelinketone, methylcyclohexanone etc.
As above-mentioned ether compound, can list: tetrahydrofuran (THF), tetrahydropyrans, morpholine, glycol dimethyl ether, diglyme, triglyme, dibutyl ether, diethyl ether, diox etc.
As above-mentioned ester compound, can list: methyl-formiate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, sec-butyl acetate, tert.-butyl acetate, pentyl acetate, Isoamyl Acetate FCC, tert.-amyl acetate, phenylacetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, the propionic acid tert-butyl ester, amyl propionate, isoamyl propionate, the propionic acid tert-pentyl ester, phenylpropionate, methyl lactate, ethyl lactate, the methoxypropionic acid methyl esters, the ethoxy-propionic acid methyl esters, the methoxy propyl acetoacetic ester, ethoxyl ethyl propionate, ethylene glycol monomethyl ether acetate, the diethylene glycol monomethyl ether acetic ester, ethylene glycol monoethyl ether acetate, the ethylene glycol ether acetic ester, glycol monomethyl isopropyl ether acetic ester, ethylene glycol monomethyl ether acetate, the secondary butyl ether acetic ester of glycol monomethyl, glycol monomethyl ethyl isobutyl ether acetic ester, glycol monomethyl uncle butyl ether acetic ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propylene glycol monopropyl ether acetic ester, propylene glycol list isopropyl ether acetic ester, the propylene glycol monobutyl ether acetic ester, the secondary butyl ether acetic ester of propylene glycol list, propylene glycol list ethyl isobutyl ether acetic ester, propylene glycol list uncle butyl ether acetic ester, the butyleneglycol methyl ether acetate, the butyleneglycol monoethyl ether acetate, butyleneglycol list propyl ether acetic ester, butyleneglycol list isopropyl ether acetic ester, butyleneglycol monobutyl ether acetic ester, the secondary butyl ether acetic ester of butyleneglycol list, butyleneglycol list ethyl isobutyl ether acetic ester, butyleneglycol list uncle butyl ether acetic ester, methyl acetoacetate, methyl aceto acetate, the ketobutyric acid methyl esters, the ketobutyric acid ethyl ester, gamma lactone, delta-lactone etc.
As above-mentioned aromatic series compounds, can list: benzene, toluene, ethylbenzene, 1, diethylbenzene, isopropyl benzene, isobutyl-benzene, methyl (sec.-propyl) benzene, tetraline, methyl-phenoxide.
As above-mentioned hydrocarbon compound, can list: 1-dicyanopropane, 1-cyano group butane, 1-cyano group hexane, cyanocyclohexanoic alkane, cyano group benzene, 1,3-dicyano propane, 1 with cyano group, 4-dicyanobutane, 1,6-dicyano hexane, 1,4-dicyano hexanaphthene, 1,4-dicyanobenzenes etc.
As the above-mentioned organic solvent that does not have hydroxyl, consider from the solvability of realization preferred concentration range and the angle of cost, be preferably ether compound, ester compound or aromatic series compounds.In addition, the organic solvent boiling point under atmospheric pressure that does not have a hydroxyl is preferably 60～180 ℃.
Film of the present invention forms with the composition of raw material according to the manufacturing film, also can contain to remove two (pentane-2,4-diketo) zinc and do not have film precursor beyond the hydrate, and its usage quantity can be set according to the composition of desirable film.
For example, under the situation of the film that contains multicomponent element by the CVD manufactured, comprise the method that method that each composition in multicomponent film precursor is gasified independently, supplies with (below be sometimes referred to as " single source method ") and the mixing raw material that obtains multicomponent film precursor is mixed with the composition of wishing in advance gasify, supply with (below be sometimes referred to as " mixing source method "), under the situation of mixing source method, it is that two (pentane-2,4-diketo) zinc do not have the mixing solutions of hydrate and other film precursor that film of the present invention forms with raw material.
Film precursor as beyond the zinc anhydride that can use in these cases has no particular limits, and can use the used known general precursor in the raw material at CVD.
As above-mentioned precursor, can list one or more organic coordination compounds and compound of metal, alkyl metal cpd, arylide etc. of alcohol compound and/or glycol compound and/or beta-diketon and/or cyclopentadiene compound, organic amine compound etc.In addition, as the metal species of precursor, can list magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, gallium, indium, germanium, tin, lead, antimony, bismuth, silicon, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium.
As can listing alkanols such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, 2-butanols, isopropylcarbinol, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, tertiary amyl alcohol as the alkylol cpd of above-mentioned organic ligand; 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2-(2-methoxy ethoxy) ethanol, 2-methoxyl group-1-methyl ethanol, 2-methoxyl group-1,1-dimethyl ethanol, 2-oxyethyl group-1,1-dimethyl ethanol, 2-isopropoxy-1,1-dimethyl ethanol, 2-butoxy-1,1-dimethyl ethanol, 2-(2-methoxy ethoxy)-1,1-dimethyl ethanol, 2-propoxy--1,1-diethyl ethanol, 2-sec-butoxy-1,1-diethyl ethanol, 3-methoxyl group-1, ether alcohol classes such as 1-dimethyl propyl alcohol; Can obtain the dialkyl amido alcohol of alkyl oxide of the present invention etc.
As can listing 1,1 as the diol compound of above-mentioned organic ligand, 2-propylene glycol, 1, ammediol, 2,4-hexylene glycol, 2,2-dimethyl-1, ammediol, 2,2-diethyl-1, ammediol, 1,3 butylene glycol, 2,4-butyleneglycol, 2,2-diethyl-1,3 butylene glycol, 2-ethyl-2-butyl-1, ammediol, 2,4-pentanediol, 2-methyl isophthalic acid, ammediol, 2-methyl-2,4-pentanediol, 2,4-hexylene glycol, 2,4-dimethyl-2,4-pentanediol etc.
As can listing methyl ethyl diketone as the beta-diketone compound of above-mentioned organic ligand, hexane-2, the 4-diketone, 5-methyl hexane-2, the 4-diketone, heptane-2, the 4-diketone, 2-methylheptane-3, the 5-diketone, 5-methylheptane-2, the 4-diketone, 6-methylheptane-2, the 4-diketone, 2,2-dimethyl heptane-3, the 5-diketone, 2,6-dimethyl heptane-3,5-diketone, 2,2,6-trimethylammonium heptane-3,5-diketone, 2,2,6,6-tetramethyl-heptane-3, the 5-diketone, octane-2, the 4-diketone, 2,2,6-trimethylammonium octane-3, the 5-diketone, 2,6-dimethyl octane-3, the 5-diketone, 2,9-dimethyl nonane-4, the 6-diketone, 2-methyl-6-ethyl decane-3, the 5-diketone, 2,2-dimethyl-6-ethyl decane-3, the beta-diketon class that alkyl such as 5-diketone replace; 1,1,1-three amyl fluorides-2,4-diketone, 1,1,1-three fluoro-5,5-dimethylhexane-2,4-diketone, 1,1,1,5,5,5-hexafluoro pentane-2,4-diketone, 1,3-two perfluoro hexyl propane-1, the beta-diketon class of fluorine substituted alkyls such as 3-diketone; 1,1,5,5-tetramethyl--1-methoxyhexane-2,4-diketone, 2,2,6,6-tetramethyl--1-methoxyl group heptane-3,5-diketone, 2,2,6,6-tetramethyl--1-(2-methoxy ethoxy) heptane-3, the beta-diketon class that ethers such as 5-diketone replace etc.
As can listing cyclopentadiene, methyl cyclopentadiene, ethyl cyclopentadiene, propyl group cyclopentadiene, sec.-propyl cyclopentadiene, butyl cyclopentadiene, sec-butyl cyclopentadiene, isobutyl-cyclopentadiene, tertiary butyl cyclopentadiene, dimethyl cyclopentadiene, tetramethyl-ring pentadiene etc. as the cyclopentadiene compound of above-mentioned organic ligand.Organic amine compound as organic ligand can list methylamine, ethamine, propylamine, Isopropylamine, butylamine, sec-butylamine, TERTIARY BUTYL AMINE, isobutylamine, dimethylamine, diethylamine, dipropyl amine, Diisopropylamine, ethylmethylamine, propyl group methylamine, isopropylmethylamine etc.As the alkyl of alkyl metal cpd, can list methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-, amyl group, tert-pentyl, isopentyl etc.As the aryl of above-mentioned metal arylide, can list phenyl, aminomethyl phenyl, 3,5-dimethylphenyl, ethylphenyl etc.
Film of the present invention forms and does not contain impurity halogen, impurity organic compositions such as impurity metal ingredient except the precursor component that constitutes it, impurity chlorine with raw material as far as possible.The impurity metal ingredient in each element preferably below the 100ppb, more preferably below the 10ppb.Be preferably below the 1ppm in total amount, more preferably below the 100ppb.The impurity halogenic ingredient is preferably below the 100ppm, more preferably below the 10ppm, more preferably below the 1ppm.The impurity organic composition is preferably below the 500ppm in total amount, more preferably below the 50ppm, more preferably below the 10ppm.In addition, when using,, therefore wish in advance as much as possible with moisture removal because moisture can become the reason that particulate (particle) in the CVD raw material of hydrate of two (pentane-2,4-diketo) zinc or the particulate in the CVD method produce as the CVD raw material.Amount of moisture is preferably below the 100ppm, more preferably below the 10ppm, more preferably below the 1ppm.
In addition, film of the present invention forms with raw material in order to reduce or prevent the particle contamination of the film of manufacturing, in the fine grain measurement that particle detector carries out in according to the scattering of light formula liquid of liquid phase, quantity greater than the particle of 0.3 μ m is preferably below 100, more preferably the quantity greater than the particle of 0.2 μ m is below 1000 in the 1ml liquid phase, quantity greater than the particle of 0.2 μ m is below 1000 in 1ml, more preferably below 100.
Film-forming method of the present invention is to make film of the present invention form steam that obtains and the reactant gas importing substrate that uses as required with other precursor vaporized of raw material and use as required, precursor is decomposed on substrate and/or chemical reaction takes place, film is grown up on substrate, sedimentary CVD method thereby make.For conveying Supply Method, the deposition method of raw material, create conditions, manufacturing installation etc., have no particular limits, can use known common condition, method etc.
As the above-mentioned reactant gas that uses as required, for example, as oxidizing gas, can list oxygen, ozone, nitrogen peroxide, nitrogen protoxide, water vapour, hydrogen peroxide, formic acid, acetate, diacetyl oxide etc., as the gas of reductibility, can list hydrogen, in addition, material as making nitride can list organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, Alkylenediamine, hydrazine, ammonia etc.Material as making sulfide can list hydrogen sulfide.
In addition, as above-mentioned deposition method, only can list by heating unstripped gas or unstripped gas and reactant gas are reacted hot CVD, the plasma CVD that uses heat and plasma body, the optical cvd that uses light and heat that makes thin film deposition, the light plasma CVD that uses heat, light and plasma body and with the deposition reaction of CVD and be divided into unit process and on the molecule rank, carry out the sedimentary ALD of substep (ald).
In addition, as above-mentioned creating conditions, can list temperature of reaction (substrate temperature), reaction pressure, sedimentation velocity etc.For temperature of reaction, the temperature that above-claimed cpd of the present invention can fully be reacted is more than 160 ℃, more preferably 250～800 ℃.In addition, reaction pressure is preferably normal atmosphere～10Pa, normal atmosphere～500Pa more preferably, the combination of deposition method and reaction pressure is arbitrarily, can list decompression hot CVD, decompression plasma CVD, decompression optical cvd, decompression light plasma CVD, normal atmosphere hot CVD, atmospheric pressure plasma CVD, normal atmosphere optical cvd, normal atmosphere light plasma CVD.Sedimentation velocity can be controlled according to supply of raw material condition (gasification temperature, vapor pressure), temperature of reaction, reaction pressure.If sedimentation velocity is big, then resulting film characteristics worsens sometimes, if little, then has problems on productivity sometimes, therefore is preferably 0.5～5000nm/ branch, more preferably 1～1000nm/ branch.In addition, under the situation of ALD, number of times that can Control Circulation is to obtain desirable thickness.
In addition, in film-forming method of the present invention, after thin film deposition,, can also carry out anneal, under the situation that needs ladder to cover, reflow process can also be set in order to obtain better electrical characteristic.Temperature under this situation is generally 500～1200 ℃, is preferably 600～800 ℃.
According to having used film of the present invention to form the film that the film-forming method manufacturing of the present invention with raw material obtains, precursor, reactant gas by suitable other compositions of selection and creating conditions can obtain the film of desirable kinds such as metal, alloy, sulfide, oxide ceramics, nitride ceramics, glass.Kind as prepared film, can list for example zinc, ZnSe, zinc oxide, zinc sulphide, zinc-indium composite oxides, add the zinc oxide of lithium, add the ferrite of zinc, lead-zinc composite oxide, lead-zinc-niobium composite oxides, bismuth-zinc-niobium composite oxides, barium-zinc-tantalum composite oxides, the tin-zinc composite oxides, as the purposes of these films, can list for example transparent conductive body, twinkler, fluor, photocatalyst, magnetic substance, electrical conductor, high dielectric, strong dielectric, piezoelectrics, microwave dielectric, optical waveguide, the light amplifier, photoswitch, the hertzian wave guard shield, solar cell etc.
Embodiment
Below, the present invention will be described in more detail by Production Example, evaluation Example and embodiment.Yet the present invention is not subjected to any restriction of following embodiment etc.
[Production Example] two (pentane-2,4-diketo) zinc does not have the manufacturing of hydrate
For commercially available two (pentane-2,4-diketo) zinc (Northeast chemical company system), remove water of hydration by the sublimation purifying operation of heating and decompression, obtaining yield and be two (pentane-2,4-diketo) zinc of 60% from 130 ℃, the cut of 30Pa does not have hydrate.For the crystal that obtains, mensuration IR,
1The ultimate analysis of H-NMR, carbon and hydrogen and TG-DTA, being accredited as two (pentane-2,4-diketo) zinc does not have hydrate.
IR measures
The IR that two (pentane-2,4-diketo) zinc does not have hydrate is illustrated in Fig. 1, and the IR that removes water of hydration commercially available two (pentane-2,4-diketo) zinc before is illustrated in Fig. 2.Among the IR figure of two (pentane-2, the 4-diketo) zinc before removing water of hydration, can confirm at 3324cm
-1Absorption with summit from water of hydration, but do not have the crystal of hydrate for removing water of hydration two (pentane-2,4-diketo) zinc afterwards, confirmed not exist this absorption.
1H-NMR measures (the deuterium benzole soln of 1 weight %)
Near 0.28ppm, do not detect the peak of the water of hydration of two (pentane-2,4-diketo) zinc hydrates.
Ultimate analysis
Two (the pentanes-2 that obtain, the 4-diketo) not have the carbon content of hydrate be 45.5 quality % (theoretical value is 45.56 quality %) to zinc, hydrogen richness is 5.3 quality % (theoretical value is 5.35 quality %), does not have the theoretical value unanimity of hydrate with two (pentane-2,4-diketo) zinc.And the carbon content of commercially available two (pentane-2,4-diketo) zinc is 42.4 quality %, and hydrogen richness is 5.9 quality %.The theoretical value of 1 hydrate is: carbon is 42.65 quality %, and hydrogen is 5.73 quality %, and is consistent with above-mentioned IR measurement result, can identify that commercially available product is 1 hydrate.
(Ar100ml/min, 10 ℃/min's TG-DTA heat up, sample size; Gained does not have hydrate 9.495mg, commercially available product 7.354mg)
Two (pentanes-2 of gained have been confirmed, the 4-diketo) zinc does not have that hydrate demonstrates because the weight in 1 stage due to the volatilization reduces, commercially available product demonstrate until 100 ℃ because the weight due to the disengaging of water of hydration reduces, the weight in 2 stages of being reduced by the weight due to the volatilization reduces.
[evaluation Example 1] volatile evaluation
Two (pentanes-2 about gained in the above-mentioned Production Example, the 4-diketo) zinc does not have hydrate, two (octane-2, the 4-diketo) zinc, two (2,2-dimethyl-6-ethyl decane-3, the 5-diketo) zinc, temperature when having measured quality 50% minimizing in the TG mensuration under the intensification condition of Ar 100ml/min, 10 ℃/min.Temperature was respectively when the quality 50% during TG under these conditions measures reduced: two (pentanes-2, the 4-diketo) not have hydrate (measuring with test material 9.495mg) be 202 ℃ to zinc, two (octanes-2, the 4-diketo) zinc (10.561mg measures with the test material) is 245 ℃, two (2,2-dimethyl-6-ethyl decane-3,5-diketo) zinc (9.282mg measures with the test material) is 263 ℃.
[evaluation Example 2] deliquescent evaluation
Two (pentanes-2 about gained in the above-mentioned Production Example, the 4-diketo) zinc does not have the hydrate two (pentanes-2 preceding with removing water of hydration, the 4-diketo) zinc, estimated the isobutyl methyl ketone, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, N-BUTYL ACETATE and the toluene that do not have the organic solvent of hydroxyl in conduct, and as the solvability in the diethylene glycol monomethyl ether of the organic solvent with hydroxyl.Evaluation is undertaken by following method: with respect to the 1000ml organic solvent, mix zinc complex, making its content is 0.1,0.2,0.3,0.5,0.7,1.0 mole, seal and leave standstill 24 hours after, confirm having or not of solid phase by visual method.Table 1 illustrates the concentration use level that remains the clear solution that does not have solid phase with respect to 1000ml.And, do not dissolve 0.1 mole usefulness "＜0.1 " and represented, dissolved 1 mole usefulness "＞1 " expression.
Table 1
| Two (pentane-2,4-diketo) zinc does not have hydrate | Remove preceding two (pentane-2, the 4-diketo) zinc of water of hydration | |
| Isobutyl methyl ketone | 0.2 mole | ＜0.1 mole |
| Tetrahydrofuran (THF) | ＞1 mole | ＜0.1 mole |
| Glycol dimethyl ether | ＞1 mole | ＜0.1 mole |
| Diglyme | 0.5 mole | ＜0.1 mole |
| N-BUTYL ACETATE | 0.3 mole | ＜0.1 mole |
| Toluene | 0.7 mole | ＜0.1 mole |
| Diethylene glycol monomethyl ether | 0.7 mole | ＜0.1 mole |
Can confirm that by table 1 two (pentane-2,4-diketo) zinc does not have hydrate various organic solvents is demonstrated sufficient solvability, does not contain solid phase, can obtain the solution of full concentration.In contrast, confirmed two (pentane-2,4-diketo) zinc for the commercially available product that contains hydrate, even 0.1 mole, in solution, also there is little powdered dissolved residue.And, collect this dissolved residue and carry out the result that IR measures, be accredited as 1 hydrate of two (pentane-2,4-diketo) zinc.
[evaluation Example 3]
Do not have hydrate solution about synthetic two (pentane-2,4-diketo) zinc in the above-mentioned evaluation Example 2,, under the intensification condition of Ar 100ml/min, 10 ℃/min, carried out the mensuration of TG-DTA for the solution of peak concentration in various organic solvents.The result who will two (pentane-2,4-diketo) zinc have the constituent that hydrate obtains with 0.7 mole mixed as the diethylene glycol monomethyl ether of the organic solvent with hydroxyl with respect to 1000ml is illustrated by Fig. 3.According to Fig. 3, can confirm 7.22% remnants down at 271.8 ℃.When using the solution of the organic solvent that does not have hydroxyl, can not confirm hinting the volatilization residue that has such reaction product, only can observe because the weight that the volatilization of organic solvent and two (pentane-2,4-diketo) zinc causes reduces.By above-mentioned phenomenon, confirmed that the hydroxyl of diethylene glycol monoethyl ether and two (pentane-2,4-diketo) zinc do not have the hydrate reaction, obtain lacking volatile reaction product.
By above-mentioned evaluation Example 1～3, two (pentanes-2 have been confirmed, the 4-diketo) zinc does not have hydrate and does not have the constituent that the constituent of the organic solvent of hydroxyl, particularly this organic solvent are ether solvent, esters solvent, aromatic series kind solvent, can obtain the stable solution under sufficient concentration, be suitable as the CVD raw material.
The manufacturing of [embodiment] zinc-oxide film
Use the CVD device shown in Fig. 4, on silicon wafer according to following condition, two (pentane-2,4-diketo) zinc that 0.5mol is obtained in above-mentioned Production Example are dissolved in the tetrahydrofuran (THF) of 1000ml and the solution that obtains forms as film and makes zinc-oxide film with raw material.The film that makes is identified the mensuration of its thickness and composition with fluorescent X-ray.
(creating conditions)
Vaporizer temperature: 140 ℃, material flow: 0.5sccm, oxygen flow: 500sccm, reaction pressure: 1000Pa, reaction times: 20 minutes, substrate temperature: 450 ℃, carrier gas: argon gas 500sccm
(result)
Thickness: 240nm, composition: zinc oxide.
Claims (4)
1. a film forms and use raw material, and it has pair (pentane-2,4-diketo) zinc that 0.1～1 mole of conduct must composition not have the solution formation of hydrate by the organic solvent dissolution that does not have hydroxyl with respect to 1000ml.
2. film as claimed in claim 1 forms and uses raw material, and wherein, the described organic solvent that does not have hydroxyl is selected from ether compound, ester cpds or aromatics.
3. film as claimed in claim 1 or 2 forms and uses raw material, and wherein, the described organic solvent boiling point under atmospheric pressure that does not have hydroxyl is 60～180 ℃.
4. film-forming method, it is to import to contain on matrix each described film in the claim 1～3 is formed the two (pentanes-2 that obtain with material gasification, the 4-diketo) zinc does not have the steam of hydrate, and this steam is decomposed and/or chemical reaction takes place and forms the film that contains zinc atom on matrix.
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| JP2006225023A JP4757143B2 (en) | 2006-08-22 | 2006-08-22 | Thin film forming raw material and thin film manufacturing method |
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| KR (1) | KR20080018126A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482113A (en) * | 2009-04-21 | 2012-05-30 | 东曹精细化工株式会社 | Composition for forming doped or non-doped zinc oxide thin film, and method for producing zinc oxide thin film using same |
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| JP2003342222A (en) * | 2002-05-23 | 2003-12-03 | Kanto Chem Co Inc | Method for producing zinc acetylacetonate monohydrate |
| JP4565897B2 (en) * | 2004-06-14 | 2010-10-20 | 株式会社Ａｄｅｋａ | Thin film forming raw material and thin film manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482113A (en) * | 2009-04-21 | 2012-05-30 | 东曹精细化工株式会社 | Composition for forming doped or non-doped zinc oxide thin film, and method for producing zinc oxide thin film using same |
| US9096441B2 (en) | 2009-04-21 | 2015-08-04 | Tosoh Finechem Corporation | Composition for manufacturing doped or undoped zinc oxide thin film and method for manufacturing zinc oxide thin film using same |
| CN102482113B (en) * | 2009-04-21 | 2015-08-26 | 东曹精细化工株式会社 | The zinc-oxide film manufacture composition of doping or undoped and use its manufacture method of zinc-oxide film |
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| JP4757143B2 (en) | 2011-08-24 |
| JP2008050623A (en) | 2008-03-06 |
| TWI439564B (en) | 2014-06-01 |
| TW200827478A (en) | 2008-07-01 |
| KR20080018126A (en) | 2008-02-27 |
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