CN101193849B - Niobium 2-ethylhexanoate derivative, process for producing the derivative, organic acid metal salt composition containing the derivative, and process for producing thin film from the composition - Google Patents
Niobium 2-ethylhexanoate derivative, process for producing the derivative, organic acid metal salt composition containing the derivative, and process for producing thin film from the composition Download PDFInfo
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Abstract
A niobium 2-ethylhexanoate derivative characterized in that it contains niobium in a proportion of 13 to 16 mass% and carbon in a proportion falling within the range of 50 to 58 mass% and consists only of niobium and oxygen atoms and 2-ethylhexyl acid residue. This derivative can be produced by reacting pentakis(alkoxy)niobium with 2-ethylhexyl acid. Further, there is provided an organic acid metal salt composition characterized by containing this derivative, a precursor of metal other than niobium and at least one organic solvent. A thin film containing a niobium element and a non- niobium metal can be produced by coating a base material with the organic acid metal salt composition and heating the same.
Description
Technical field
The present invention relates to have the 2 ethyl hexanoic acid niobium derivative of ad hoc structure, the manufacture method of this derivative, the organic acid metal salt composition that contains 2 ethyl hexanoic acid niobium derivative, the metal precursor except that niobium and organic solvent, and the manufacture method of using the film of said composition.
Background technology
The ceramic membrane that contains the ceramic membrane of niobium element or contain niobium element and lead element is applied to various uses because of having special electrical characteristic and be studied.Especially be used to use the electronic component of the electronic component such as high dielectric capacitor, ferroelectric condenser, gate insulating film, barrier film, piezoelectric element of the feature of excellent dielectric characteristic.For example, in non-patent literature 1, reported that the part of the titanium of lead titanate-zirconate is substituted by niobium Doped with Titanium lead zirconates (PNZT) film of niobium.
As the manufacture method of aforesaid film, can enumerate MOD such as coating thermal decomposition method and sol-gel method (Metal Organic Deposition: method, CVD (Chemical Vapour Deposition: chemical vapour deposition) method, ALD (AtomicLayer Deposition: method etc. ald) deposition of metal organic).For the lower film of working accuracy, low cost of manufacture, film form and be easy to the MOD method is the method that is fit to.The precursor that is used for the film of MOD method mainly uses alkoxy compound, metal salts of organic acids, and the niobium precursor uses alkoxy compound, metal salts of organic acids too.
In addition, in patent documentation 1, disclosed mixed-metal compounds in organic solvent, made solution metal ratio of components (mol ratio) represent that with A: B: C=X: Y: Z (wherein, A represents Sr and Ba and/or Pb, B represents Bi, C represents Ta and/or Nb) time, satisfy 0.4≤X≤1.0,1.5≤Y≤3.5, Z=2, with Sr: Ba: Pb=a: b: when c represents, satisfy 0.7X≤a＜X, 0＜b+c≤0.3X, form the Bi ferro-electric film and form with composition (claim 1).In addition, in [0024] of patent documentation 1 paragraph, as niobium compound, illustration alkoxide such as ethanol niobium, propyl alcohol niobium, butanols niobium, 2-methyl cellosolve niobium, with carboxylate salts such as sad niobium, n-caproic acid niobium, 2 Ethylbutanoic acid niobium, isovaleric acid niobium etc., as lead compound, illustration alkoxide such as carboxylate salt such as lead octoate 36, n-caproic acid lead, 2 Ethylbutanoic acid lead, isoamyl lead plumbate, lead acetate and ethanol lead, propyl alcohol lead, butanols lead etc.
In addition, in patent documentation 2, disclosed to have to form and used Bi
2(Ta
mNb
1-m)
2O
8The substrate layer of the thick 5～50nm of (wherein, 0≤m≤1) expression and be formed at composition on this substrate layer with (Sr
XBi
1-X) Bi
2(Ta
YNb
1-Y)
2O
ZThe Bi ferro-electric film (claim 1) of the main stor(e)y of (still, 0.4≤X≤1,0≤Y≤1, Z are the total of each metallic element institute with oxygen atomicity) expression and have composition Bi
2(Ta
mNb
1-m)
2O
8(wherein, 0≤m≤1) expression, the substrate layer of thick 5～50nm and being formed on this substrate layer is formed with [{ Sr
X(Pb and/or Ba
n}
XBi
1-X] Bi
2(Ta
YNb
1-Y)
2O
ZThe Bi ferro-electric film (claim 2) of the main stor(e)y of (still, the total of 0＜n≤0.3,0.4≤X≤1,0≤Y≤1, the Z oxygen atomicity of enclosing for each metallic element) expression.In addition, in [0025] of patent documentation 2 paragraph, as niobium compound, illustration alkoxide such as ethanol niobium, propyl alcohol niobium, butanols niobium, 2-methyl cellosolve niobium, with carboxylate salts such as sad niobium, n-caproic acid niobium, 2 Ethylbutanoic acid niobium, isovaleric acid niobiums, as lead compound, illustration alkoxide such as carboxylate salt such as lead octoate 36, n-caproic acid lead, 2 Ethylbutanoic acid lead, isoamyl lead plumbate, lead acetate and ethanol lead, propyl alcohol lead, butanols lead etc.
In addition, in patent documentation 3, disclosed the method that is used to make electronic component, it comprises providing and contains perovskite typed A-bit position, the operation of a plurality of polyoxyalkylated metal parts of perovskite typed beta-position part and superlattice generating portion, this method is by this each metal partly and is in order had multilayer (116,124,128) step that stackedization super crystal lattice material (112) makes up according to corresponding correlation proportion, described multiwalled are in proper order for being selected from A-position metal, the beta-position metal, and the A/B (124) with ionic subunit of A/B unit (146) of the oxide compound of the metal of their mixture formation, have superlattice and generate the unitary superlattice generation layers of ionic subunit (116), the perovskite typed AB layer (128) that contains A-position metal and beta-position metal; Present method is characterised in that and may further comprise the steps: the step that contains the perovskite typed AB layer with perovskite typed oxygen octahedra lattice different with the lattice of above-mentioned A/B layer; This precursor solution is coated in operation on the substrate; By this precursor solution on this substrate is handled, form have this A/B layer, operation that mixolimnion that these superlattice generate layer and this perovskite typed AB layer dissolves lattice material.In addition, in the 47th page embodiment 4 of patent documentation 3, putting down in writing: the raw material as pre-precursor solution uses the 2 ethyl hexanoic acid niobium.
Patent documentation 1: the spy opens flat 9-25124 communique, claims [0024]
Patent documentation 2: the spy opens flat 9-142845 communique, claims [0025]
Patent documentation 3: the flat 11-509683 communique of special table, the 47th page of claims
Non-patent literature 4:Jpn.Appl.Phys., Vol.44, (2005) 267～274 pages of No.1A
Summary of the invention
The problem that invention will solve
Aforesaid organic acid niobium, according to manufacture method and creating conditions, the character of gained derivative, rerum natura have very big-difference, as the precursor of MOD method, have the problem that is difficult to handle.In addition, one of problem of MOD method is that for the coating fluid composition that contains precursor, it is difficult obtaining sufficient stability.In order to form the ceramic membrane of multicomponent system, composition as coating liquid, formed the mixing solutions that contains the precursor of multiple metallic element in the film, for example, when using metallic alkoxide compound as precursor compound, because metallic alkoxide compound is rich reactive, therefore with other precursor or atmosphere in reactions such as moisture, the thickening gelation takes place or form the precipitation iso-metamorphism.These are rotten to coated technique with membranous detrimentally affect arranged.In addition, because the state (shape and electrical characteristic) of gained film depends on the combination of precursor, therefore, be difficult to find the suitableeest combination that solves the aforementioned stable problem.For example, known, as the precursor of titanium or zirconium, alkoxy compound can provide the fine film, still, when it mixes with other precursor component, be difficult to reach can be durable storage stability.
Generally, the organic acid niobium is expressed as (RCOO) mostly
5Nb, still, carbon content, Nb content all have varied.In fact, the combining unit that forms the organic acid niobium is " RCOO-Nb and Nb-O-Nb ", " RCOO-Nb and Nb=O " or " RCOO-Nb, Nb-O-Nb and Nb=O ", for example, expression is during with the model of simple structure representative, shown in following chemical formula, in fact, be difficult to correctly identify chemical structure.Illustrated that in following chemical formula, L represents organic acid residue.
Wherein, for example, have and be similar to by five niobium alkoxides and organic acid reaction gained (RCOO)
5The storage stability of the carbon content that Nb forms, the organic acid niobium derivative of Nb content is poor.In addition, the known easy residual alkoxyl group of organic acid niobium derivative that is obtained by five niobium alkoxides is considered to be actually the compound that is made of RCOO-Nb, Nb-O-Nb, Nb-OR ' (OR ' be the alkoxyl group from raw material).In addition, also think to have (RCOO)
5The storage stability of the compound of Nb structure itself is poor.On the other hand, the molecular weight of the organic acid niobium derivative that the Nb-O-Nb chain in the molecule is big, content of niobium increase, and carbon content reduces.Because the solvability variation of such organic acid niobium derivative, therefore, spendable solvent and concentration thereof are restricted, that is, deliquescent boundary narrows down.In addition, with other metal precursor and time spent, in the gained film, the niobium oxides skewness, so, can not form the even composition of expection and the part of crystalline texture and increase, the gained film does not reach the electrical characteristic of expection.
In addition, will be near Nb[C
4H
9CH (C
2H
5) COO]
5The 2 ethyl hexanoic acid niobium of theoretical value, promptly the coating liquid that uses as precursor of the organic acid niobium of content of niobium about 11.5 quality % exists the problem of storage stability difference.In addition, such organic acid niobium is mixing with other precursor compound when using again, also exists because of chemical reaction to make the coating lyogelization or produce problems such as precipitation.
Therefore, the objective of the invention is to, provide as the precursor of MOD method useful 2 ethyl hexanoic acid niobium derivative and manufacture method thereof.
In addition, another object of the present invention is to, when adopting the MOD method to make to contain the film of niobium and the metal except that niobium, provide to be suitable for the manufacture method of MOD method with the film of the organic acid metal salt composition that contains niobium precursor and the metal precursor except that niobium of raw material and use said composition.
The method of dealing with problems
The inventor etc. found that after furtheing investigate repeatedly: the 2 ethyl hexanoic acid niobium derivative with ad hoc structure can address the above problem, thereby finishes the present invention.
That is, 2 ethyl hexanoic acid niobium derivative of the present invention is characterised in that, content of niobium is at 13～16 quality %, and carbon content and only is made of niobium atom, Sauerstoffatom and 2 ethyl hexanoic acid residue in the scope of 50～58 quality %.
In addition, above-mentioned 2 ethyl hexanoic acid niobium derivative can so that the reaction of five (alkoxyl group) niobiums and 2 ethyl hexanoic acid make under the feature.
In addition, the invention provides the organic acid metal salt composition and be characterised in that, contain above-mentioned 2 ethyl hexanoic acid niobium derivative; Metal precursor except that niobium; At least a kind of organic solvent.
In addition, organic acid metal salt composition of the present invention can contain other metal precursor arbitrarily.
In addition, the manufacture method of the film on the matrix of the present invention is characterized in that the above-mentioned organic acid metal salt composition of coating on matrix by heating, forms the film that contains niobium element and the metal except that niobium.
Description of drawings
Fig. 1 is by this 2 ethyl hexanoic acid niobium derivative of embodiment 1 gained
1H-NMR analyzes collection of illustrative plates.
Fig. 2 is by embodiment 1 gained 2 ethyl hexanoic acid niobium of the present invention derivative
13C-NMR analyzes collection of illustrative plates.
Fig. 3 is the IR analysis collection of illustrative plates by embodiment 1 gained 2 ethyl hexanoic acid niobium of the present invention derivative.
Fig. 4 is the TG-DTA analysis collection of illustrative plates by embodiment 1 gained 2 ethyl hexanoic acid niobium of the present invention derivative.
Embodiment
The content of niobium of 2 ethyl hexanoic acid niobium derivative of the present invention at 13～16 quality %, be preferably in the scope of 13～15 quality %, carbon content at 50～58 quality %, be preferably in the scope of 52～57 quality %, and only constitute by niobium atom, Sauerstoffatom and 2 ethyl hexanoic acid residue.Illustrated that the content of niobium of the theoretical value of 2 ethyl hexanoic acid niobium is 11.5 quality %, carbon content is 59.4 quality %.
At this, when content of niobium is lower than 13 quality %, because of the storage stability variation not preferred, in addition, when surpassing 16 quality %, because of deliquescent boundary narrows down not preferred.In addition, when carbon content is lower than 50 quality %, because of deliquescent boundary narrow down not preferred, in addition, when surpassing 58 quality %, because of the storage stability variation not preferred.
Being characterized as of 2 ethyl hexanoic acid niobium derivative of the present invention is liquid, storage stability is good, good, the deliquescent boundary of mixed stability is wide, therefore, is useful as the precursor of MOD method.Such feature also helps to become the component selections 2 ethyl hexanoic acid as organic acid.
For example, be that the few organic acid niobium derivative of carbon number of organic acid composition has solidified tendency with acetate or valeric acid etc., be difficult to obtain stable coating liquid.In addition, since low to the solvability of organic solvent, deliquescent abundant boundary therefore be can not get.In addition, the problem that produces unhappy stink is arranged.In addition, because the content of niobium of the carbon number of organic acid composition organic acid niobium derivative how is few, therefore the solvability that converts for mole can not get sufficient deliquescent boundary sometimes.In addition, such organic acid niobium derivative is used for the film that precursor obtains, impurity carbon residue increases.
The manufacture method of 2 ethyl hexanoic acid niobium derivative of the present invention is as starting raw material, five (alkoxyl group) niobium is used for the method for raw material.As the method that five (alkoxyl group) niobium is used for raw material, can enumerate and add the method that 2 ethyl hexanoic acid heats; The water byproduct that generates during with five (alkoxyl group) niobiums and 2 ethyl hexanoic acid reaction is removed, and uses the method for dewatering agent simultaneously.In addition, the reaction ratio of five (alkoxyl group) niobiums and 2 ethyl hexanoic acid is, with respect to 1 mole of five (alkoxyl group) niobium, 2 ethyl hexanoic acid 3～8 moles, be preferably in 4～6 moles the scope.At this, when the 2 ethyl hexanoic acid amount was lower than 3 moles, alkoxyl group was residual, and the storage stability variation is therefore not preferred, in addition, when being higher than 8 moles, can not bring into play with the effect that addition increases, and economic benefit is unfavorable, and is therefore not preferred.
In addition, in the manufacture method of 2 ethyl hexanoic acid niobium derivative of the present invention, with regard to five (alkoxyl group) niobium that uses as starting raw material, can for example alkoxy compound of carbon numbers 1～4 such as five (methoxyl group) niobium, five (oxyethyl group) niobium, five (propoxy-) niobium, five (isopropoxy) niobium, five (butoxy) niobium be shown example.
In addition, when five (alkoxyl group) niobium is used as starting raw material, because when having water in the reaction system, the Nb-O-Nb chainpropagation, therefore the control of reaction becomes difficult.Therefore, as the manufacture method of 2 ethyl hexanoic acid niobium derivative of the present invention, the preferred dewatering agent that consumes water byproduct that uses.As above-mentioned dewatering agent, can enumerate acid anhydrides such as diacetyl oxide, maleic anhydride, citraconic anhydride, malonic anhydride, itaconic anhydride, Tetra hydro Phthalic anhydride, succinyl oxide, ortho-formiates such as triethyl orthoformate, trimethyl orthoformate etc.Wherein, owing to being easy to be preferably acid anhydrides after the reaction, most preferably be diacetyl oxide by removing in the reaction system.In addition, the usage quantity of dewatering agent is with respect to as 1 mole of five (alkoxyl group) niobium of raw material, is 0.5～10 mole, is preferably in 1～8 mole the scope.When the consumption of dewatering agent is lower than 0.5 mole, sometimes can not show and use effect, therefore not preferred; In addition, when surpassing 10 moles, along with the effect of the increase of addition can not be brought into play, economic benefit is unfavorable, and is therefore not preferred.
In addition, in the manufacture method of 2 ethyl hexanoic acid niobium derivative of the present invention, temperature of reaction 100～150 ℃, be preferably in 110～140 ℃ the scope.At this, when temperature of reaction is lower than 100 ℃, for finishing the reaction needed spended time, and there is alkoxyl group residual in the resultant, therefore not preferred; In addition, when surpassing 150 ℃, it is difficult that the control that responds becomes, and the control of molecular weight, content of niobium becomes difficult situation, and is therefore not preferred.
As can enumerating for example niobium oxides, niobium-tantalum pentoxide (Ta according to using 2 ethyl hexanoic acid niobium derivative of the present invention, using the film of MOD with the MOD manufactured of raw material
2-XNb
XO
5) wait thin dielectric film; Piezoelectricity body thin films such as Lithium niobium trioxide; Niobium-bismuth tantalate [Bi
2(Ta
mNb
1-m)
2O
5], niobium-bismuth tantalate strontium (Sr
1-XBa
XTa
2-yNb
yO
9), ferroelectric membranc such as niobium Doped with Titanium lead plumbate, niobium doped bismuth titanate, niobium Doped with Titanium lead plumbate, niobium Doped with Titanium lead zirconates.
When 2 ethyl hexanoic acid niobium derivative of the present invention is used as the raw material of the MOD method of above-mentioned film, 2 ethyl hexanoic acid niobium derivative of the present invention can be used as the composition that contains organic solvent and precursor compound as required etc., and described precursor compound can be introduced other elements in film.The form of said composition can be emulsion, suspension, dispersion liquid, colloidal dispersion, solution wantonly a kind, preferably makes the solution that can form composition homogeneity film good and in apparent good order and condition and uses.In addition, the content of the 2 ethyl hexanoic acid niobium derivative in the said composition is preferably in the scope of 5～40 quality % in the scope of 1～50 quality % of matrix coating being easy to usually.
Organic acid metal salt composition of the present invention is characterised in that, contains above-mentioned 2 ethyl hexanoic acid niobium derivative, metal precursor except that niobium and at least a kind of organic solvent as essential composition as the niobium precursor, also can contain other metal precursor as required.In addition, organic acid metal salt composition of the present invention is useful as the raw material of being made the film of glass or pottery by the MOD method of coating thermal decomposition method or sol-gel method and so on matrix.
As the metal species of the metal precursor except that niobium, can enumerate periodictable 1 family's elements such as lithium, sodium, potassium, rubidium, caesium; Periodictable 2 family's elements such as beryllium, magnesium, calcium, strontium, barium; Periodictable 3 family's elements such as scandium, yttrium, lanthanon (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), actinide elements; Periodictable 4 family's elements such as titanium, zirconium, hafnium; Periodictable such as vanadium, tantalum 5 family's elements; Periodictable 6 family's elements such as chromium, molybdenum, tungsten; Periodictable 7 family's elements such as manganese, technetium, rhenium; Periodictable 8 family's elements such as iron, ruthenium, osmium; Periodictable 9 family's elements such as cobalt, rhodium, iridium; Periodictable 10 family's elements such as nickel, palladium, platinum; Periodictable 11 family's elements such as copper, silver, gold; Periodictable 12 family's elements such as zinc, cadmium, mercury; Periodictable 13 family's elements such as aluminium, gallium, indium, thallium; Periodictable 14 family's elements such as silicon, germanium, tin, lead; Periodictable 15 family's elements such as arsenic, antimony, bismuth; Periodictables such as polonium 16 family's elements.In addition, as other metal precursor, can enumerate metal salts of organic acids, metallic alkoxide compound, β-diketone metal complexes, 'beta '-ketoester metal complexes etc.
2 ethyl hexanoic acid niobium derivative of the present invention is useful as the precursor with the film of lead and usefulness.Therefore, in organic acid metal salt composition of the present invention, the metal precursor except that niobium that is particularly suitable for 2 ethyl hexanoic acid niobium derivative and usefulness is plumbous precursor, particularly the organic acid lead compound.
Above-mentioned organic acid lead compound is different with above-mentioned 2 ethyl hexanoic acid niobium derivative, has usefulness (RCOO) basically
2The structure that general formulas such as Pb are represented.In addition, the organic acid lead compound also contains crystal water sometimes.The organic acid lead compound that the present invention uses both can be a hydrate, also can be anhydride because and other precursor of usefulness react with water and make mixed stability and storage stability variation sometimes, so be preferably anhydride.
As the organic acid that constitutes organic lead sulfate compound, be preferably the aliphatics organic acid of carbon number 2～18, for example can enumerate acetate, propionic acid, butyric acid, isopropylformic acid, valeric acid, caproic acid, sad, 2 ethyl hexanoic acid, n-nonanoic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, palmitinic acid, margaric acid, stearic acid, linolic acid, gamma-linolenic acid, linolenic acid, ricinoleate acid, 12-oxystearic acid etc.
At this, also there is solid form in the organic acid lead compound that is obtained by less aliphatics organic acid salts of carbon number such as acetate, propionic acid, valeric acids, as MOD method raw material, is difficult to the organic acid metal salt composition that provides abundant and stable sometimes.In addition, because the organic acid lead compound that is obtained by this aliphatics organic acid is low with respect to the solvability of organic solvent, so can not get deliquescent abundant boundary sometimes.On the other hand, owing to the lead content of the organic acid lead compound that is obtained by the many aliphatics organic acids of carbon numbers such as stearic acid is little, therefore the solvability that converts for mole also can not get sufficient solvability scope sometimes.In addition, the impurity carbon residue that will be used for the film that precursor obtains by the organic acid lead compound that this aliphatics organic acid obtains increases sometimes.In addition, as the organic acid that constitutes organic lead sulfate compound, stay in grade and can cheap to obtain be necessary.Therefore, as the organic acid that constitutes organic lead sulfate compound, be preferably the aliphatics organic acid of carbon number 6～12, more preferably 2 ethyl hexanoic acid.
The organic acid lead compound is not had any different because of its manufacture method, can use the organic acid lead compound that adopts known manufacture method to obtain, but be preferably in the precursor the not organic acid lead compound of halogen-containing impurity, therefore, being preferably with plumbous oxide, lead acetate, two (alkoxyl group) lead is the organic acid lead compound that raw material is made.
In addition, in organic acid metal salt composition of the present invention, the blending ratio of 2 ethyl hexanoic acid niobium derivative and organic acid lead compound is not particularly limited, and can cooperate according to purposes.For example, when the precursor as the film of dielectric medium or piezoelectrics used, metal molar was than for respect to 1 mole of niobium atom, lead atom 0.01～10 mole, be preferably in 0.1～5 mole the scope.
Then, the used organic solvent of organic acid metal salt composition of the present invention is described.
As the organic solvent that uses in the organic acid metal salt composition of the present invention, can enumerate pure series solvent, polyvalent alcohol series solvent, ketone series solvent, ester series solvent, ether series solvent, polyethers series solvent, aliphatics or clicyclic hydrocarbon series solvent, aromatic hydrocarbons series solvent, the hydrocarbon solvent with cyano group, other solvent etc., they can use to mix more than a kind or 2 kinds and use.
As pure series solvent, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-butanols, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, 2-amylalcohol, neopentyl alcohol, tertiary amyl alcohol, hexanol, 2-hexanol, enanthol, 2-enanthol, octanol, 2-Ethylhexyl Alcohol, sec-n-octyl alcohol, cyclopentanol, hexalin, suberyl alcohol, methylcyclopentanol, methyl-cyclohexanol, methyl cycloheptanol, benzylalcohol, 2-methyl cellosolve, butoxy ethanol, 2-(2-methoxy ethoxy) ethanol, 2-(N, the N-dimethylamino) ethanol, 3-(N, N-dimethylamino) propyl alcohol etc.
As the polyvalent alcohol series solvent, can enumerate ethylene glycol, propylene glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, neopentyl glycol, isobutyl glycol (3-methyl isophthalic acid, the 3-butyleneglycol), 1,2-hexylene glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,2-ethohexadiol, ethohexadiol (2-ethyl-1, the 3-hexylene glycol), 2-butyl-2-ethyl-1, ammediol, 2,5-dimethyl-2,5-hexylene glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol etc.
As the ketone series solvent, can enumerate acetone, butanone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), ethyl butyl ketone, two acetone, diisobutyl ketone, Methyl amyl ketone, pimelinketone, methylcyclohexanone etc.
As the ester series solvent, can enumerate 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 the ether series solvent, can enumerate tetrahydrofuran (THF), tetrahydropyrans, morpholine, glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dme, dibutyl ether, diethyl ether, two
Alkane etc.
As aliphatics or clicyclic hydrocarbon series solvent, can enumerate pentane, hexane, hexanaphthene, methylcyclohexane, dimethyl cyclohexane, ethylcyclohexane, heptane, octane, perhydronaphthalene, solvent naphtha etc.
As the aromatic hydrocarbon series solvent, can enumerate benzene, toluene, ethylbenzene, dimethylbenzene, sym-trimethylbenzene, diethylbenzene, isopropyl benzene, Isobuytel Benzene, isopropyl toluene, 1,2,3,4-tetralin.
As hydrocarbon system solvent, can enumerate 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 other organic solvent, can enumerate N-N-methyl-2-2-pyrrolidone N-, methyl-sulphoxide, dimethyl formamide.
The content of the organic solvent in the organic acid metal salt composition of the present invention is not particularly limited, and can cooperate according to purposes.When using organic acid metal salt composition of the present invention, be in the scope of 20～99 quality %, and when in the scope of 40～95 quality %, can provide good screening characteristics as the raw material of MOD method.
In addition, above-mentioned organic solvent can select those to demonstrate sufficient solvability with respect to precursor, and uses easy organic solvent as the coating solvent.In the above-mentioned organic solvent, pure series solvent is preferred because the coating solvent as various matrixes such as silicon substrate, metallic matrix, ceramic matrix, glass basis, resin matrixes demonstrates good screening characteristics, more preferably butanols.In addition, when using mixed solvent, also being preferably with the butanols is the mixed solvent of principal constituent, more preferably uses to contain the above mixed solvent of butanols 50 quality %.
In addition, organic acid metal salt composition of the present invention also can contain above-mentioned illustrative metal precursor arbitrarily except containing the preferred organic lead sulfate compound of 2 ethyl hexanoic acid niobium derivative and the metal precursor except that niobium.
As employed other metal precursor, particularly titanium, zirconium, lanthanon, bismuth, tantalum beyond the metal precursor except that niobium of the 2 ethyl hexanoic acid niobium derivative that contains in organic acid metal salt composition of the present invention and organic acid lead compound and so on is useful.
Precursor as above-mentioned titanium, zirconium, hafnium, can enumerate by alkylol cpd deutero-four alkoxy compounds such as methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, 2-butanols, isopropylcarbinol, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, tertiary amyl alcohol, 2-methyl cellosolve, butoxy ethanol, 2-(dimethylamino) ethanol, by the aliphatics organic acid deutero-metal salts of organic acids of illustrative carbon number 2～18 in the explanation of above-mentioned organic acid niobium derivative; As the precursor of lanthanon, bismuth, can enumerate by above-mentioned alkylol cpd deutero-tri-alkoxy compound the aliphatics organic acid deutero-metal salts of organic acids of illustrative carbon number 2～18 in the explanation by above-mentioned organic acid lead compound; As the precursor of tantalum, can enumerate by above-mentioned alkylol cpd deutero-five alkoxy compounds the aliphatics organic acid deutero-metal salts of organic acids of illustrative carbon number 2～18 in the explanation by above-mentioned organic acid lead compound.
Organic acid metal salt composition of the present invention, when metal precursor uses unsettled metal alkoxide compound such as four (alkoxyl group) titaniums or four (alkoxyl group) zirconium arbitrarily as other, can provide to be difficult for producing precipitation or gelation takes place, and stable organic acid metal salt composition.
Then, the manufacture method to film of the present invention describes.
The manufacture method of film of the present invention adopts the MOD method that the organic acid metal salt composition of above-mentioned explanation is used for raw material.The condition of MOD method etc. is not particularly limited, and can use known method.For example, representational method is included in the working procedure of coating of coating organic acid metal salt composition of the present invention on the matrix, with with matrix or whole heating and film forming heat-agglomerating operation, as required, between working procedure of coating and heat-agglomerating operation, also can introduce drying process with the solvent seasoning in the composition of coating, or the calcination process that under the temperature lower than sintering circuit, heats, also can after sintering circuit, introduce annealing operation.In addition, for obtaining necessary thickness, but by above-mentioned working procedure of coating to operation repeatable operation arbitrarily repeatedly.For example, but repeatable operation whole operations repeatedly from working procedure of coating to sintering circuit, but also repeatedly working procedure of coating and drying process and/or calcination process of repeatable operation.
As the coating method in the above-mentioned working procedure of coating, can enumerate that spin-coating method, dip coating, spraying method, levelling Lacquer finish coating process (mist coating method), flow coat method, curtain coating method, rolling method, cutter are coated with method, rod is coated with method, screen painting method, ink jet method, spread coating etc.
Temperature in the above-mentioned drying process is preferably 50 ℃～200 ℃, more preferably 80 ℃～150 ℃.In addition, the temperature in the calcination process is preferably 150 ℃～600 ℃, more preferably 200 ℃～400 ℃.In addition, the temperature in the sintering circuit is preferably 400 ℃～1000 ℃, more preferably 450 ℃～800 ℃.In addition, the temperature in the annealing operation is preferably 450 ℃～1200 ℃, more preferably 600 ℃～1000 ℃.
Above-mentioned calcination process, sintering circuit promote under the purpose that film forms or improve the condition of surface of film and the purpose of electrical characteristic under, can under all gases atmosphere, implement.As this gas, can enumerate oxygen, ozone, water, carbonic acid gas, hydrogen peroxide, nitrogen, helium, hydrogen, argon etc.
According to the present invention, the precursor of the MOD method good as the solvability to organic solvent, that stable solution can be provided when mixing with other precursor compound plays the effect of the 2 ethyl hexanoic acid niobium derivative that can obtain to be fit to.
In addition, according to the present invention, raw material as the MOD method, the organic acid metal salt composition that contains niobium and the metal except that niobium, preferred plumbous precursor with good storage stability can be provided, in addition, the film-forming method that said composition is used for the MOD method of raw material can obtain the uniform film of quality.
In addition, use the organic acid metal salt composition of the present invention of 2 ethyl hexanoic acid derivative of the present invention, precursor in the time of can being suitable as by MOD manufactured film, for example, can be used for forming lead niobate, niobium Doped with Titanium lead plumbate, niobium Doped with Titanium lead plumbate, niobium Doped with Titanium lead zirconates, niobium/bismuth tantalate/strontium/lead, niobium/bismuth tantalate/strontium/barium/films such as lead use, these films are the films that can be used as suitable uses such as dielectric device, ferroelectric cell, piezoelectric element.
Embodiment
Below, enumerate embodiment and comparative example is described more specifically the present invention.In addition, the present invention should not be construed as qualifications such as being subjected to following embodiment.
The manufacturing of embodiment 1:2-thylhexoic acid niobium derivative No.1
Under the exsiccant argon gas atmosphere, 0.5 mole of five (oxyethyl group) niobium, dry toluene 200ml pack in reaction flask, add 2.6 moles of diacetyl oxides, 2.6 moles of 2 ethyl hexanoic acids therein, after 120 ℃ of bath temperature refluxed 4 hours down, bathing under warm 135 ℃, toluene and low-boiling point material are removed in distillation from reaction system, the 3～1Torr that reduces pressure in the system are concentrated again, and obtain yellow viscous liquid 345g thus.The gained yellow viscous liquid is implemented following mensuration:
(1) ultimate analysis
Interpolation will be heated to 100 ℃ of powder that obtain as Nb with respect to 63% nitric acid aqueous solution of 45 times of sample qualities
2O
5Carry out quantitatively, the result, content of niobium is 13.7 quality %.
In addition, carbon and hydrogen richness are analyzed by the CHN ultimate analysis, the result, C content is that 55.1 quality %, H content are 8.3 quality %.
(2) spectroscopic analysis
1H-NMR analyzes: the gained collection of illustrative plates is shown in Fig. 1.By shown in Figure 1
1The collection of illustrative plates that H-NMR analyzes can confirm not exist alkoxyl group.
13(solvent: heavy benzol): the gained collection of illustrative plates is shown in Fig. 2 to C-NMR.Can confirm not exist alkoxyl group by collection of illustrative plates shown in Figure 2.In addition, the carbon peak of observing the 2 ethyl hexanoic acid residue respectively has a plurality of.This shows the 2 ethyl hexanoic acid residue that exists multiple environment.
IR (coating process): the gained collection of illustrative plates is shown in Fig. 3.Can be by collection of illustrative plates shown in Figure 3 at 1500～1600cm
-1Observe many places and absorb, at 1400～1500cm
-1Also observing many places absorbs.This shows and exists multiple COONb.
(3) heat is analyzed
TG-DTA (air 300ml/ minute, heat-up rate: 10 ℃/minute, sample size 38.8037mg, with reference to aluminum oxide: 7.1320mg): the gained collection of illustrative plates is shown in Fig. 4.
The manufacturing of comparative example 1:2-thylhexoic acid niobium derivative No.2.
Under the exsiccant argon gas atmosphere, pack in reaction flask 0.5 mole of columbium pentachloride, ethanol 200ml add 2.6 moles of 2 ethyl hexanoic acids, stir 2 hours being blown under the ammonia.The stop supplies ammonia is being bathed after 80 ℃ of temperature refluxed 4 hours down, refluxes under the argon gas 1 hour being blown into again.With the reaction solution cool to room temperature,, solvent is replaced with toluene by ethanol, the ammonium chloride that filtering separation is separated out to by decant and the solution that removes by filter ammonium chloride.This solution after toluene and low-boiling point material are removed in 135 ℃ of following distillations of bath temperature, is concentrated the 3～1Torr that reduces pressure in the system again, obtain yellow viscous liquid 345g.Gained yellow viscous liquid and the foregoing description 1 are carried out ultimate analysis equally, and content of niobium is 12.2 quality %, and carbon content is 59.0 quality %.
The manufacturing of comparative example 2:2-thylhexoic acid niobium derivative No.3
Under the exsiccant argon gas atmosphere, 0.5 mole of five (oxyethyl group) niobium, dry dimethylbenzene 200ml pack in reaction flask, add 2.6 moles of 2 ethyl hexanoic acids therein, after 145 ℃ of bath temperature refluxed 4 hours down, bathing under warm 145 ℃, distillation removes removal xylene and low-boiling point material from reaction system, the 3～1Torr that reduces pressure in the system is concentrated again, and obtains yellow viscous liquid 335g thus.Gained yellow viscous liquid and the foregoing description 1 are carried out ultimate analysis equally, and content of niobium is 17.4 quality %, and carbon content is 53.0 quality %.
Estimate 1
To 2 ethyl hexanoic acid niobium derivative No.1～3 that obtain by the foregoing description 1, comparative example 1 and comparative example 2, use toluene and butanols, estimate the solvability in organic solvent.Organic solvent 6g and the mixed table 1 that the results are shown in of 2 ethyl hexanoic acid niobium derivative 4g.
Table 1
| ? | 2 ethyl hexanoic acid niobium derivative No.1 | 2 ethyl hexanoic acid niobium derivative No.2 | 2 ethyl hexanoic acid niobium derivative No.3 |
| Toluene | Dissolving | Dissolving | Indissoluble, separation |
| Butanols | Dissolving | Dissolving | Indissoluble, separation, gonorrhoea |
Estimate 2
To 2 ethyl hexanoic acid niobium derivative No.1～2 that obtain by the foregoing description 1 and comparative example 1, use the tetrahydrofuran solution of five (oxyethyl group) tantalum, 0.6 mol, carry out the mixed stability test.10ml has been added 50% the solution that 2 ethyl hexanoic acid niobium derivative to the mole number of niobium is a tantalum in the alkoxyl group tantalum solution, or the solution that 10ml does not add 2 ethyl hexanoic acid niobium derivative joins in the sample bottle of 20ml, after in 30 ℃, the constant temperature and humidity cabinet of humidity 50%, preserving 18 hours, the state of observation sample.The results are shown in table 2.
Table 2
| ? | 2 ethyl hexanoic acid niobium derivative No.1 | 2 ethyl hexanoic acid niobium derivative No.2 | Do not add 2 ethyl hexanoic acid niobium derivative |
| After 18 hours | Clear solution | Little turbid, precipitation | Little turbid, precipitation |
According to The above results, can confirm the favorable solubility of 2 ethyl hexanoic acid niobium derivative of the present invention with respect to organic solvent, in addition, also good with the mixed stability of other precursor compound.Can confirm to have the effect that makes ethanol tantalum have stability in addition.Otherwise, the 2 ethyl hexanoic acid niobium derivative that content of niobium is many poorly soluble, the 2 ethyl hexanoic acid niobium derivative that content of niobium is few and the mixed stability of other precursor compound are poor.
This shows: 2 ethyl hexanoic acid niobium derivative of the present invention demonstrates special excellent results as the precursor of MOD method.
Embodiment 2
To be dissolved in the butanols by 2 ethyl hexanoic acid niobium derivative No.1 and the 2 ethyl hexanoic acid lead that the foregoing description 1 obtains, preparation niobium and plumbous metal molar ratio are that 1: 1, niobium and plumbous total metal ingredient concentration are the organic acid metal salt composition 1 of 0.1 mol.
Comparative example 3
Use five (oxyethyl groups) except that niobium except replacing 2 ethyl hexanoic acid niobium derivative, preparation cooperates the organic acid metal salt composition 2 of the relatively product of (metal molar ratio, metal ingredient conversion concentration) equally with the foregoing description 2.
Estimate 3
The organic acid metal salt composition 2 of the relatively product that the organic acid metal salt composition 1 of the present invention's product that 10ml is obtained by the foregoing description 2,10ml are obtained by above-mentioned comparative example 3 adds the sample bottle of 20ml respectively, observes the state of the sample preserve 18 hours in 30 ℃, the constant temperature and humidity cabinet of humidity 50% after.Found that organic acid metal salt composition 1 is transparent, and organic acid metal salt composition 2 muddinesses, precipitation.
Estimate 4
The organic acid metal salt composition 2 of the relatively product that obtain to the organic acid metal salt composition 1 of the present invention's product of being obtained by the foregoing description 2 with by comparative example 3 uses TG-DTA to estimate the thermolysis courses.Condition determination at TG-DTA is an environmental gas: air, and 300ml/ minute, temperature program(me): 30 ℃～600 ℃ of useful ranges, heat-up rate: 10 ℃/minute, reference: implement under the condition of aluminum oxide 7.575mg.Sample size is, organic acid metal salt composition 1 is 23.6935mg, and organic acid metal salt composition 2 is 24.3817mg.
Consequently, for the DTA of organic acid metal salt composition 1, observing with 291 ℃ is 1 wide cut exothermic peak on summit; For the DTA of organic acid metal salt composition 2, observe with 294 ℃ and be the wide cut exothermic peak on summit and be the wide cut exothermic peak on summit with 321 ℃.
Frequently the storage stability of the organic acid metal salt composition 2 of product is better can to confirm the organic acid metal salt composition 1 of the present invention's product by above-mentioned evaluation 3.In addition, according to estimating 4, organic acid metal salt composition 1 is observed 1 thermolysis peak, and organic acid metal salt composition 2 is observed 2 thermolysis peaks.This shows: in organic acid metal salt composition 1, thermolysis takes place in 2 ethyl hexanoic acid niobium derivative and 2 ethyl hexanoic acid plumbous derivative simultaneously, and in organic acid metal salt composition 2, demonstrates the niobium precursor and plumbous precursor decomposes respectively.This shows: contain the material of MOD method of the film of composition metal as manufacturing, the film composition homogeneity of the film that is obtained by organic acid metal salt composition 1 is good.
Embodiment 3
To be dissolved in the butanols by 2 ethyl hexanoic acid niobium derivative No.1,2 ethyl hexanoic acid lead, four (isopropoxy) titanium and four (butoxy) zirconium that the foregoing description 1 obtains, the metal molar ratio of preparation niobium, lead, titanium, zirconium is 1: 1: 0.5: 0.5, the total metal ingredient concentration of niobium, lead, titanium and zirconium is the organic acid metal salt composition 3 of the present invention's product of 0.1 mol.
Comparative example 4
Use five (oxyethyl groups) except that niobium except replacing 2 ethyl hexanoic acid niobium derivative, preparation cooperates the organic acid metal salt composition 4 of the relatively product of (metal molar ratio, metal ingredient conversion concentration) equally with the foregoing description 1.
Comparative example 5
Four (isopropoxy) titaniums and four (butoxy) zirconium are dissolved in the butanols, and the metal molar ratio of preparation titanium and zirconium is that the total metal ingredient concentration of 1: 1, titanium and zirconium is the organic acid metal salt composition 5 of the relatively product of 0.05 mol.
Estimate 5
The organic acid metal salt composition 4,5 of the relatively product that the organic acid metal salt composition 3 of the present invention's product that 10ml is obtained by the foregoing description 3,10ml are obtained by above-mentioned comparative example 4 and comparative example 5 adds the sample bottle of 20ml respectively, observes the state of the sample preserve 18 hours in 30 ℃, the constant temperature and humidity cabinet of humidity 50% after.The result observes, and organic acid metal salt composition 3 is transparent, organic acid metal salt composition 4 and 5 muddinesses, precipitation.
According to above-mentioned evaluation Example 5, frequently the organic acid metal salt composition 4 of product and 5 storage stability are better for the organic acid metal salt composition 3 that can confirm the present invention's product.
Embodiment 4
Organic acid metal salt composition 3 that use is obtained by the foregoing description 3 and the organic acid metal salt composition 4 that is obtained by above-mentioned comparative example 4 according to following working order, form film on 6 inches silicon chips.To the gained film, with the naked eye the result with 100 times polarization optical microscopic examination condition of surface is: the film quality that is obtained by organic acid metal salt composition 3 is even, does not observe crack, agglutinator and pinhole.Find that by the film that the organic acid metal salt composition 4 of product relatively obtains the part gonorrhoea is arranged, observe agglutinator and crack.
Working order
With organic acid metal salt composition 2ml curtain coating on silicon chip, under 500rpm, implement rotary coating under 15 seconds the condition under 5 seconds, 1500rpm.Silicon chip was heated 30 seconds on 100 ℃ hot-plate, make solvent seasoning, return to room temperature after 2 minutes in calcining under 300 ℃.After implementing rotary coating, drying, calcining, cooling 3 times repeatedly, on electric furnace,, carry out sintering 600 ℃ of heating 3 minutes down.
Can confirm that by the foregoing description 4 using the film of organic acid metal salt composition 3 of the present invention is films that quality has superperformance uniformly.
Claims (11)
1.2-thylhexoic acid niobium derivative, it is the niobium derivative of pentavalent, it is characterized in that, content of niobium is at 13～16 quality %, and carbon content and only is made of niobium atom, Sauerstoffatom and 2 ethyl hexanoic acid residue in the scope of 50～58 quality %,
It is obtained by five (alkoxyl group) niobiums and 2 ethyl hexanoic acid reaction, and described alkoxyl group is the alkoxyl group of carbon number 1～4.
2. the described 2 ethyl hexanoic acid niobium of claim 1 derivative wherein, with respect to 1 mole of five (alkoxyl group) niobium, reacts in the presence of dewatering agent for 4～6 moles with 2 ethyl hexanoic acid, and described alkoxyl group is the alkoxyl group of carbon number 1～4.
3. the described 2 ethyl hexanoic acid niobium of claim 2 derivative wherein, with respect to 1 mole of five (alkoxyl group) niobium, uses 1～8 mole of dewatering agent, and described alkoxyl group is the alkoxyl group of carbon number 1～4.
4. claim 2 or 3 described 2 ethyl hexanoic acid niobium derivatives, wherein, with respect to 1 mole of five (alkoxyl group) niobium, the diacetyl oxide that uses 4～6 moles is as dewatering agent, and described alkoxyl group is the alkoxyl group of carbon number 1～4.
5. the described 2 ethyl hexanoic acid niobium of claim 1 derivative, wherein, temperature of reaction is in 100～150 ℃ scope.
6. the organic acid metal salt composition is characterized in that, contains the described 2 ethyl hexanoic acid niobium of claim 1 derivative, the metal precursor except that niobium and at least a kind of organic solvent,
Described metal precursor is metal salts of organic acids, metallic alkoxide compound, β-diketone metal complexes or 'beta '-ketoester metal complexes.
7. the described organic acid metal salt composition of claim 6, wherein, the content of the organic solvent in the composition is in the scope of 20～99 quality %.
8. claim 6 or 7 described organic acid metal salt compositions, wherein, the metal precursor except that niobium is with general formula (RCOO)
2The organic acid lead compound that Pb represents, in the formula, R represents the aliphatic alkyl of carbon number 1～17.
9. the described organic acid metal salt composition of claim 8, wherein, the organic acid lead compound is a 2 ethyl hexanoic acid lead.
10. the described organic acid metal salt composition of claim 9 wherein, according to the metal molar ratio, with respect to 1 mole of niobium atom, contains lead atom with 0.01～10 mole ratio.
11. on matrix, make the method for film, it is characterized in that each described organic acid metal salt composition in the coating claim 6～10 by heating, forms the film that contains niobium element and the metal except that niobium on matrix.
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| JP2005171441A JP2006342138A (en) | 2005-06-10 | 2005-06-10 | Niobium 2-ethylhexanoate derivative and its preparation method |
| PCT/JP2006/310737 WO2006132107A1 (en) | 2005-06-10 | 2006-05-30 | Niobium 2-ethylhexanoate derivative, process for producing the derivative, organic acid metal salt composition containing the derivative, and process for producing thin film from the composition |
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| Ce′lia Machado Ronconi,et al..Structural evolution and optical properties ofCd2Nb2O7 films prepared by metallo-organic decomposition..Thin Solid Films.441.2003,441121-129. * |
| Jang-Sik Lee,et al..Effect of low-energy accelerated ion bombardment onthe properties of metal-organic decomposition derived SrBi2(Ta,Nb)2O9 thin films processed at low temperature..Journal of the American Ceramic Society.87 4.2004,87(4),720-723. * |
| Jang-SikLee et al..Effect of low-energy accelerated ion bombardment onthe properties of metal-organic decomposition derived SrBi2(Ta |
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