CN1699186A - Preparation method of stable water-soluble niobium and tantalum precursor and application thereof - Google Patents
Preparation method of stable water-soluble niobium and tantalum precursor and application thereof Download PDFInfo
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- CN1699186A CN1699186A CN200410014962.9A CN200410014962A CN1699186A CN 1699186 A CN1699186 A CN 1699186A CN 200410014962 A CN200410014962 A CN 200410014962A CN 1699186 A CN1699186 A CN 1699186A
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- 239000002243 precursor Substances 0.000 title claims abstract description 51
- 239000010955 niobium Substances 0.000 title claims abstract description 45
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 33
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 33
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 41
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 9
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 8
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- OSYUGTCJVMTNTO-UHFFFAOYSA-D oxalate;tantalum(5+) Chemical compound [Ta+5].[Ta+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OSYUGTCJVMTNTO-UHFFFAOYSA-D 0.000 claims description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 7
- 229910012463 LiTaO3 Inorganic materials 0.000 claims description 6
- 229910019695 Nb2O6 Inorganic materials 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- YJEJFHCHLNUCBH-UHFFFAOYSA-A 2-hydroxypropane-1,2,3-tricarboxylate niobium(5+) Chemical compound [Nb+5].[Nb+5].[Nb+5].OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O YJEJFHCHLNUCBH-UHFFFAOYSA-A 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229910001460 tantalum ion Inorganic materials 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000003916 acid precipitation Methods 0.000 claims description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 16
- 239000010408 film Substances 0.000 description 13
- 229920001940 conductive polymer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- -1 niobium ions Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 2
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HJSAVSHUKKYRIX-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;niobium Chemical compound [Nb].OC(=O)CC(O)(C(O)=O)CC(O)=O HJSAVSHUKKYRIX-UHFFFAOYSA-N 0.000 description 1
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PILOURHZNVHRME-UHFFFAOYSA-N [Na].[Ba] Chemical compound [Na].[Ba] PILOURHZNVHRME-UHFFFAOYSA-N 0.000 description 1
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000002821 niobium Chemical class 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 229920000334 poly[3-(3'-N,N,N-triethylamino-1-propyloxy)-4-methylthiophene-2,5-diyl hydrochloride] polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003481 tantalum Chemical class 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of stable water-soluble niobium and tantalum precursor, which comprises using pentoxide of tantalum or niobium as raw material, mixing columbium pentachloride or ttantalum pentachloride with potassium hydroxide or sodium hydroxide, grinding homogeneously, carrying out incandesce reacting 2-4 hours at 400-550 deg. C, obtaining fusing agent of potassium (sodium) niobate or potassium (sodium) tantalite, dissolving the fluxing agent into deionized water, filtering the solution till the solution shows strong acidity (pH<2), so that the niobium or tantalum in the solution can be fully precipitated in the form of niobic acid or tantalic acid. Finally charging right amount of citric acid water solution into columbic acid or charging right amount of oxalic acid into tantalic acid deposition, thus obtaining water-soluble niobium precursor or oxalate aqueous solution of tantalum.
Description
Technical Field
The present invention relates to a process for the preparation of stable water-soluble niobium and tantalum precursors and their use in the preparation of ferroelectric thin films and powders.
Background
Ferroelectric materials (e.g. Sr)xBa1-xNb2O6(SBN)，LiNbO3，LiTaO3，SrBi2Ta2O9(SBT)SrBi2Nb2O9) Is an important functional material, has the effects of ferroelectricity, piezoelectricity, pyroelectric, electrooptical, acoustooptic, nonlinear optics and the like, and has wide application prospect in the fields of microelectronics and optoelectronics. The wet Chemical method comprises a sol-gel method (So1-gel), a metallorganic decomposition (MOD) method, a Chemical Solution Deposition (CSD) method and the like, and the prepared film and powder have the characteristics of uniform micro-area component height, accurate stoichiometric ratio, easy doping, easy large-area film forming, low equipment investment cost, simple process, suitability for industrial application and the like, and are one of the technologies which have practical application value and important scientific research value in the existing film preparation method.
Tantalum ethoxide and niobium ethoxide are prepared by wet chemical method (sol-gel method and metallorganic decomposition method) to synthesize ferroelectric compound (such as Sr) containing tantalum or niobiumxBa1-xNb2O6(SBN)，LiNbO3，LiTaO3，SrBi2Ta2O9，SrBi2Nb2O9) The most commonly used precursor materials. Generally, tantalum and niobium have nearly identical methods in the preparation of precursors for the above ferroelectric materials, since tantalum and niobium are both group VA transition elements, and have comparable atomic radii and very similar properties. However, the major drawbacks of the alkoxide-based processes are that tantalum ethoxide and niobium ethoxide are expensive, extremely moisture sensitive, require a strictly dry environment during formulation, usually in a glovebox (Glove box), and some chemical reactions require Schlenk vacuum lines. The prepared precursor solution also needs to be waterproof during storage, and the service life is short. Although some improvements, such as the use of ligands such as ethylene glycol methyl ether instead of alkoxy groups, have been used to partially improve the stability of the precursor, this problem has not been solved fundamentally and the commercial application of similar precursor systems has been greatly limited. Tantalum pentachloride, niobium pentachloride have also been used as precursors for tantalum or niobium, although they are less expensive and have improved stability relative to alkoxides, but they are not acceptableThe small amount of chlorine left in the final material to be avoided may deteriorate the material-related photoelectric properties.
Disclosure of Invention
The purpose of the invention is: a method for preparing stable water-soluble niobium and tantalum precursors is provided and the precursors are used in ferroelectric thin films and powder fabrication. The invention also aims to provide a method which has low raw material cost and simple process, is suitable for industrial application and ensures the quality of the ferroelectric film preparation.
The purpose of the invention is realized as follows: the method comprises the steps of using tantalum or niobium pentoxide as a raw material, mixing and grinding the niobium pentoxide or the tantalum pentoxide and potassium hydroxide or sodium hydroxide uniformly according to a certain molar ratio, putting the mixture into a corundum crucible, and carrying out a burning reaction at 400-550 ℃ for 2-4 hours to obtain a melt of potassium (sodium) niobate or potassium (sodium) tantalate. Dissolving the melt in deionized water, filtering to obtain clear solution, adding proper amount of acetic acid, and precipitating to obtain white niobic acid (Nb)2O5·nH2O) or tantalic acid precipitation (Ta)2O5·nH2O), and adjusting the pH value (the pH value is less than 4) to ensure that the niobium or the tantalum in the solution is completely precipitated in the form of the niobic acid or the tantalic acid. After filtration, the white precipitate is washed repeatedly with deionized water to remove residual potassium or sodium ions adsorbed by the precipitate. Finally, adding a proper amount of Citric Acid (CA) aqueous solution into the niobic Acid precipitate or adding a proper amount of Oxalic Acid (OA) aqueous solution into the tantalic Acid precipitate, wherein the molar ratio of Oxalic Acid to tantalum ions is 1: 20-60, and dissolving the niobic Acid or the tantalic Acid to obtain a stable water-soluble niobium precursor (niobium Citric Acid aqueous solution) or a water-soluble tantalum precursor (tantalum oxalate aqueous solution).
The core of the present invention is to obtain an extremely stable water-soluble precursor of tantalum or niobium by a simple and feasible synthesis route using two inexpensive and stable raw materials, tantalum pentoxide and niobium pentoxide. The invention is characterized in that: using this precursor, Sr is preparedxBa1-xNb2O6(SBN)，LiNbO3，LiTaO3，SrBi2Ta2O9(SBT)SrBi2Nb2O9The precursor solution has excellent stability and can prepare phase-pure ferroelectric film or ferroelectric powder at lower process temperature. The method has simple process and has important application prospect in the field of integrated ferroelectrics and optoelectronics.
Drawings
FIG. 1 shows SBN75 powder of the present invention annealed at 600 deg.C for 2 hours (a) and deposited on Pt/TiO2/SiO2XRD pattern of SBN60 thin film on/Si substrate annealed at 750 deg.C for 2 hours (b).
FIG. 2 is a TEM photograph of SBN50 powder obtained by heat treatment at 700 ℃ for 2 hours according to the present invention, and the grain size is 20-40 nm.
FIG. 3 is LiNbO of the present invention3DSC curve of xerogel (baked at 150 ℃ for 4 hours), and strong exothermic peak suggests LiNbO3The crystallization temperature is about 480 ℃.
FIG. 4 shows LiNbO of the present invention heat-treated at 600 ℃ for 2 hours3XRD spectrum of the powder.
FIG. 5 is a LiNbO of the present invention3Heat treating the powder at 500 ℃ for 2 hours (a), and LiNbO3TEM and SEM photographs of films heat-treated on Si wafers at 650 ℃ for 2 hours (b).
FIG. 6 shows LiTaO heat-treated at 600 ℃ for 2 hours according to the present invention3XRD spectrum of the powder.
FIG. 7 shows LiTaO formed by heat treatment at 600 ℃ for 2 hours according to the present invention3TEM image of the powder of (5).
Detailed Description
1. Examples of the precursor synthesis of water-soluble niobium:
synthesizing raw materials: niobium pentoxide (analytically pure, 99.5%), potassium or sodium hydroxide (analytically pure), nitric acid (analytically pure), citric acid (analytically pure).
Water-soluble niobiumSynthesis route of the precursor: mixing niobium pentoxide and potassium hydroxide or sodium hydroxide according to the molar ratio of 1: 2-20, grinding uniformly, placing into a corundum crucible, and performing an ignition reaction at 400-550 ℃ for 2-4 hours, such asThe potassium niobate melt is obtained after 2.5 to 3 hours of burning reaction at 450 ℃. Dissolving the melt in deionized water, filtering to obtain clear solution, adding proper amount of acetic acid, and precipitating to obtain white niobic acid (Nb)2O5·nH2O), adjusting the pH value again to make the solution acidic (the pH value is less than 4), and completely precipitating niobium in the solution in the form of niobic acid. After filtration, the white precipitate is washed repeatedly with deionized water to remove residual potassium or sodium ions adsorbed by the precipitate. And finally, adding a proper amount of Citric Acid (CA) aqueous solution into the niobic Acid precipitate, dissolving the niobic Acid into Citric Acid under the condition that the molar ratio of the Citric Acid to niobium ions is 1: 2-10 under the heating and stirring condition of 60 ℃, and filtering to obtain the stable niobium citrate aqueous solution. The niobium content of the solution can be calibrated by gravimetric methods or by plasma coupled resonance spectroscopy (ICP).
The above examples show no significant differences between niobium pentoxide and potassium hydroxide or sodium hydroxide in molar ratios of 1: 2 and 1: 15.
The reaction equation is as follows:
ICP and gravimetric calibration results, as shown in table one: the contents of niobium ions calibrated by the two methods are basically consistent, the residual potassium ions and other impurity ions are very low, and the content of the niobium ions reaches 99 percent and is consistent with the purity of the used raw materials.
| ICP results | Nb(mmol/g) | ||||||
| Element(s) | Nb | K | Si | Na | Al | ICP | Gravimetric method |
| Content (wt.) | 99.1％ | 0.55％ | 0.21％ | 0.03％ | 0.11％ | 0.0485 | 0.0412 |
2. Precursor synthesis technical route of water-soluble tantalum:
synthesizing raw materials: tantalum pentoxide (analytical grade 99.5%), potassium hydroxide (analytical grade), nitric acid (analytical grade), oxalic acid (analytical grade)
The synthesis route of the water-soluble tantalum precursor is shown in the following reaction formula: tantalum pentoxide and potassium hydroxide or sodium hydroxide are mixed and ground uniformly (excessive alkali) according to the molar ratio of 1: 2-20, the mixture is placed into a corundum crucible, and the mixture is subjected to an ignition reaction at 400-550 ℃ for 2-4 hours, for example, at 450 ℃ for 2.5-3 hours, so as to obtain a melt of the potassium hydroxide or sodium hydroxide of the tantalum pentoxide. Dissolving the melt in deionized water, filtering to obtain clear solution, adding proper amount of acetic acid to precipitate white tantalic acid, regulating pH tomake the solution acidic (pH less than 4), and completely precipitating tantalum in the solution in the form of tantalic acid. After filtration, the white precipitate was repeatedly rinsed with deionized water to remove residual adsorbed potassium or sodium ions. And finally, adding a proper amount of Oxalic acid (Oxalic acid, OA) aqueous solution into the tantalum acid precipitate, wherein the molar ratio of Oxalic acid to tantalum ions is 20-60, dissolving the tantalum acid into the Oxalic acid under the condition of heating and stirring at 60 ℃, and filtering to obtain a stable tantalum oxalate aqueous solution. The tantalum content of the solution can be calibrated by gravimetric methods or by plasma coupled resonance spectroscopy (ICP). The above examples show no significant difference between tantalum pentoxide and potassium hydroxide or sodium hydroxide in molar ratios of 1: 2 and 1: 15.
The reaction equation is as follows:
ICP and gravimetric calibration results, as shown in table two: the contents of tantalum ions calibrated by the two methods are basically consistent, the residual potassium ions and other impurity ions are very low, and the content of the tantalum ions reaches 99 percent and is consistent with the purity of the used raw materials.
| ICP results | Ta(mmol/g) | ||||||
| Element(s) | Ta | K | Si | Na | Al | ICP | Gravimetric analysis Method of |
| Content (wt.) | 99.3％ | 0.22％ | 0.13％ | 0.03％ | 0.32％ | 0.0439 | 0.0425 |
3. Use of synthetic water-soluble tantalum or niobium precursors for the production of ferroelectric thin films and powders
A series of ferroelectric tantalum or niobium containing films or powders can be prepared using water soluble tantalum or niobium precursors. Strontium barium niobate Sr like niobate seriesxBa1-xNb2O6(SBN), lithium niobate LiNbO3Potassium sodium niobate (KNa) NbO3Barium sodium niobate (Ba)2NaNb2O5) Strontium bismuth niobate SrBi2Nb2O9Tantalate-based lithium tantalate LiTaO such as lead magnesium niobate (PMNT)3Lithium tantalate niobate (LiTa)xNb1-xO3) Potassium tantalate niobate (KTa)xNb1-xO3) Strontium bismuth tantalate SrBi2Ta2O9(SBT), and the like.
The preparation of the precursor solution and the preparation process of the film and powder are illustrated below:
preparation of SBN precursor solution: according to the chemical formula SrxBa1-xNb2O6(SBN, x is 0.25-0.75, SBN corresponding to x is 0.50, 0.60 and 0.75 is abbreviated as SBN50, SBN60 and SBN75 respectively), strontium acetate (or strontium nitrate or strontium carbonate) and barium acetate (or barium nitrate or barium carbonate) in a metered ratio are added into a water-soluble precursor solution of niobium citrate, the content of citric acid is adjusted, the molar ratio of metal ions to citric acid is adjusted to be 1: 1-10, ethylenediamine is added to adjust the pH value to be 7-8, a proper amount of ethylene glycol is added as a complexing agent (the molar ratio of the ethylene glycol to the citric acid is 1-6), heating is carried out at 80-130 ℃, magnetic stirring is carried out, most of water is removed, and polyesterification is carried out to obtain a light yellow viscous liquid. And adding a proper amount of formic acid to adjust the viscosity of the solution to 10-40 cps. The result is indistinguishable when citric acid is in excess.
3-2.LiNbO3Preparation of precursor solution: adding lithium acetate (or lithium nitrate or lithium carbonate) in a metering ratio into a water-soluble precursor solution of niobium citrate, adjusting the content of citric acid to ensure that the molar ratio of metal ions to the citric acid is between 1 to (1-10), adding ethylenediamine to adjust the pH value to be between 7-8, adding a proper amount of glycol as a complexing agent (the molar ratio of the glycol to the citric acid is between 1-6), heating at 80-130 ℃, magnetically stirring, removing most of water, and performing polyesterification to obtain a light yellow viscous liquid. The viscosity of the solution is adjusted to 10-40 cps by adding a proper amount of formic acid or acetic acid.
3-3.LiTaO3Preparation of precursor solution: adding lithium acetate (or lithium nitrate or lithium carbonate) in a metering ratio into a water-soluble tantalum oxalate precursor solution, adjusting the content of citric acid to ensure that the molar ratio of metal ions to the citric acid is between 1 to (1-10), adding a proper amount of glycol as a complexing agent (the molar ratio of the glycol to the citric acid is between 1-6), heating at 80-130 ℃, magnetically stirring, removing most of water, polyesterifying to obtain colorless viscous liquidAnd (4) liquid. The viscosity of the solution is adjusted by adding a proper amount of formic acid or acetic acidThedegree is 10-40 cps.
Substrate material: commercial monocrystalline or platinized silicon wafers, commercial ITO conductive glass, or quartz glass or monocrystalline MgO or sapphire substrates.
Preparing a film: directly depositing the precursor solution by spin-coating or dip-coating, and heat-treating the film at 200-500 deg.C. This process is repeated to obtain the desired film thickness. Finally, annealing the film at 600-800 ℃ for 1-2 hours to obtain a crystalline film.
Powder preparation: and drying the precursor solution at 180 ℃, carrying out thermal decomposition for 2-4 hours at 450 ℃, and annealing for 1-2 hours at 550-800 ℃ to obtain crystalline powder.
The effects of the invention also include: the stable niobium series (e.g. SBN, LiNbO) ferroelectric material is prepared by using water-soluble tantalum or niobium precursor3And SrBi2Nb2O9) Tantalum series (e.g. LiTaO)3And SrBi2Ta2O9) Using these precursor solutions, single-phase ferroelectric thin films are obtained on different substrates at lower heat treatment temperatures. Using these precursor solutions, single-phase ferroelectric powders are obtained at lower heat treatment temperatures. The method has simple process and has important application prospect in the field of integrated ferroelectrics and optoelectronics.
Claims (5)
1. A preparation method of stable water-soluble niobium and tantalum precursor is characterized in that tantalum or niobium pentoxide is used as a raw material, niobium pentoxide or tantalum pentoxide and potassium hydroxide or sodium hydroxide are mixed and ground uniformly according to the molar ratio of 1: 2-20, the mixture is placed into a corundum crucible, and the mixture is subjected to firing reaction at 400-550 ℃ for 2-4 hours to obtain a melt of potassium (sodium) niobate or potassium (sodium) tantalate; dissolving the melt in deionized water, filtering to obtain clear solution, adding proper amount of acetic acid, and precipitating to obtain white niobic acid (Nb)2O5·nH2O) or tantalic acid precipitation (Ta)2O5·nH2O), adjusting the pH value with nitric acid to make the solution have strong acidity (pH is less than 2), and completing the niobium or tantalum in the form of niobic acid or tantalic acidThe whole precipitate is obtained; after filtering, repeatedly washing the white precipitate with deionized water to remove residual potassium ions or sodium ions adsorbed by the precipitate; adding a proper amount of citric acid aqueous solution into the niobic acid precipitate or adding a proper amount of oxalic acid aqueous solution into the tantalic acid precipitate, wherein the molar ratio of oxalic acid to tantalum ions is 1: 20-60, so as to obtain a water-soluble niobium precursor or tantalum oxalate aqueous solution.
2. The method of preparing stable water soluble niobium and tantalum precursors of claim 1 wherein said aqueous solution of oxalic acid is added, said oxalic acid is dissolved in said tantalum acid under heating and stirring at 40-80 ℃, and said solution is filtered to obtain a stable aqueous solution of tantalum oxalate.
3. The use of the stabilized water-soluble niobium and tantalum precursors of claim 1 wherein an aqueous solution of the oxalate salt of the water-soluble niobium precursor or tantalum is used to prepare the SBN precursor solution: according to the chemical formula SrxBa1-xNb2O6Adding strontium acetate, strontium nitrate or strontium carbonate, barium acetate or barium nitrate or barium carbonate in a metered ratio into a water-soluble precursor solution of niobium citrate, adjusting the content of citric acid to ensure that the molar ratio of metal ions to the citric acid is 1: 1-10, adding ethylenediamine to adjust the pH value to be 7-8, adding a proper amount of ethylene glycol as a complexing agent, heating at 80-130 ℃, magnetically stirring, removing most of water, and polyesterifying to obtain a faint yellow viscous liquid.
4. The use of the stabilized water-soluble niobium and tantalum precursors of claim 1 wherein the aqueous solution of water-soluble niobium precursor is used to prepare LiNbO3Precursor solution or LiTaO3Precursor solution: adding lithium acetate, lithium nitrate or lithium carbonate in a metering ratio into a water-soluble precursor solution of niobium citrate, adjusting the content of citric acid to ensure that the molar ratio of metal ions to the citric acid is 1: 1-10, adding ethylenediamine to adjust the pH value to be 7-8, adding a proper amount of glycol as a complexing agent, heating at 80-130 ℃, magnetically stirring, removing most of water, and performing polyesterification to obtain a light yellow viscous liquid.
5. The use of the stabilized water-soluble niobium and tantalum precursors of claim 1 wherein the water-soluble tantalum oxalate solution is used to prepare LiTaO3Preparation of precursor solution: adding lithium acetate and lithium nitrate or lithium carbonate in a metering ratio into a water-soluble tantalum oxalate precursor solution, adjusting the content of citric acid to ensure that the molar ratio of metal ions to the citric acid is 1: 1-10, adding a proper amount of glycol as a complexing agent, heating at 80-130 ℃, magnetically stirring, removing most of water, and polyesterifying to obtain a colorless viscous liquid.
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