CN1584112A - Preparation of double axial structured CeO2 film from inorganic salt as raw material by liquid phase chemical process - Google Patents
Preparation of double axial structured CeO2 film from inorganic salt as raw material by liquid phase chemical process Download PDFInfo
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- CN1584112A CN1584112A CN 200410042624 CN200410042624A CN1584112A CN 1584112 A CN1584112 A CN 1584112A CN 200410042624 CN200410042624 CN 200410042624 CN 200410042624 A CN200410042624 A CN 200410042624A CN 1584112 A CN1584112 A CN 1584112A
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- 229910017053 inorganic salt Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000002994 raw material Substances 0.000 title claims description 13
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title abstract description 5
- 239000007791 liquid phase Substances 0.000 title abstract 2
- 238000001311 chemical methods and process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 104
- 150000000703 Cerium Chemical class 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 238000004528 spin coating Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 238000007669 thermal treatment Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 230000001737 promoting effect Effects 0.000 claims description 10
- 239000003352 sequestering agent Substances 0.000 claims description 10
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
- 238000003618 dip coating Methods 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229940074391 gallic acid Drugs 0.000 claims description 6
- 235000004515 gallic acid Nutrition 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 lanthanum aluminate Chemical class 0.000 claims description 5
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 239000005084 Strontium aluminate Substances 0.000 claims description 3
- LQDYEDBILDZMPB-UHFFFAOYSA-N [Nd].[Ca] Chemical compound [Nd].[Ca] LQDYEDBILDZMPB-UHFFFAOYSA-N 0.000 claims description 3
- PACGUUNWTMTWCF-UHFFFAOYSA-N [Sr].[La] Chemical compound [Sr].[La] PACGUUNWTMTWCF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000084 colloidal system Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229960000583 acetic acid Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 108010025899 gelatin film Proteins 0.000 description 2
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- 239000012071 phase Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A process for preparing biaxial-texture CeO2 thin film by inorganic salt material liquid phase chemical method includes: dehydrating and pre-treating for inorganic salt and organic solvent, preparing coating liquid, coating CeO2 on base, and pyrolyzing and sintering to obtain biaxial-texture CeO2. Its advantages include good crystal lattice matching performance and chemical stability, and good oxygen dispersing resistant ability.
Description
Technical field
The invention belongs to superconducting film material technology of preparing scope, particularly a kind ofly prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Thin-film technique.
Background technology
Cerium oxide (CeO
2) be a kind of multifunctional material that has a extensive future, be used to various fields such as optics, chemical catalysis, chemical color, high-temperature superconductor, chemical sensor, fuel cell.For general Application Areas, CeO
2Film only need have certain thickness, homogeneity, compactness and surface finish get final product preferably, and these are used CeO
2The orientation of film does not have particular requirement.But in the preparation process of focus-YBCO coating conductor that superconducting material is studied, generally need CeO
2Film had both had the surface of good situation, had good biaxial texture orientation again.
The coherence length of YBCO superconducting phase is very little, and crystal boundary becomes the weak connection of intrinsic.In case grain orientation is stochastic distribution in the YBCO superconducting film, a large amount of big angle crystal boundaries just forms weak the connection in the film so, even the YBCO superconducting phase itself has good superconduction transport property, because the existence of weak connection, form " bottleneck " of current delivery at the crystal boundary place, also can seriously reduce superconducting critical current density.The result of study that people such as D.Dimos report in document " Physical ReviewB 41 (1990) 4038-4050 " shows in the YBCO material, when the crystal boundary misorientation increases to 5 °, current density that can be by crystal boundary has only the crystal boundary misorientation is controlled at the electric current transmission performance that just can obtain below 2 ° than the intracrystalline current density order of magnitude that descended.Obtain can practical application high critical current densities YBCO superconductive long strip, must make the grain formation good biaxial texture orientation of YBCO (being that crystal grain all has good orientations at the c axle with in the a-b axial plane).
Early stage research concentrates on adopts evaporating deposition technique and chemical gaseous phase depositing process to deposit the YBCO superconducting film on single crystal substrates, and this film is subjected to the restriction of single crystal substrates, is unsuitable for making superconducting coil, superconducting magnet and superconductivity wire.In the face of superconducting power transmission system and superconduction forceful electric power application great demand, recently, people begin the YBCO high-temperature superconducting thin film is deposited in the substrate of flexible metal, form the compound long band of the superconduction with certain anti-adaptability to changes.This method generally is that the YBCO superconducting layer is deposited on the nickel-base strip, but owing at high temperature between nickel-base strip and the YBCO superconducting layer mutual diffusion and chemical reaction taking place, reaction product is with the superconductivity of havoc YBCO, thereby need between Ni base band and YBCO superconducting layer, introduce buffer layer, with the inhibition diffusion, and play the effect of mating lattice, reducing thermal stresses.
Buffer layer in the YBCO coating conductor is the multilayer film structure of sandwich type normally, and according to the difference of cushioning layer material system, buffer layer thin film usually has different sedimentary sequences and thickness.Buffer layer thin film material system commonly used comprises CeO
2, YSZ, Y
2O
3, SrTiO
3, LaMnO
3Deng.CeO
2Because and better chemical, lattice match between nickel-base strip and the YBCO superconducting layer, and composition is simple, the texture degree is good, is extensively thought the buffer layer that is applicable to the YBCO coating conductor.Preparation CeO
2The method of film can be divided into vacuum method and antivacuum method.The vacuum method of preparation biaxial texture thin film of ceria comprises pulsed laser deposition, electron beam evaporation, chemical vapour deposition, magnetron sputtering, ion beam assisted depositing etc., can obtain thickness at tens CeO to hundreds of nanometer, even compact by these methods
2Film, and the halfwidth of the biaxial texture of film generally all needs vacuum apparatus generally all less than 10 ° but vacuum method prepares film, cost is higher, and sedimentation rate is lower, and realizes that there is certain degree of difficulty in the extensive industrialization of high-level efficiency.
With respect to vacuum method deposition CeO
2That film, antivacuum method have is with low cost, equipment is simple, film growth rates is fast, easy control of components, is convenient to extensive industrialization.Present antivacuum method prepares CeO
2Thin film study get often be sol-gel method.
Sol-gel method prepares CeO
2Film also can be divided into two big classes, and a class is that the organic salt that utilizes cerium is joined glue, filmed, thermal treatment, finally obtains CeO
2Film.This method has been utilized the characteristic of the easy network compound key of organic cerium salt, parameters such as colloidal viscosity, extent of polymerization are easy to carry out modification and control by adding different types of organic solvent, when utilizing this colloid to film, has wetting property preferably between colloid and the substrate, the film that forms has the comparison homogeneous thickness, the crystal grain diameter of film is less, arrive between the hundreds of nanometer tens, film and heat treatment process parameter by control, can obtain good biaxial texture at metal or ceramic surface.But it is rare earth element that the problem of the maximum of this method is cerium, though China raw-material big producing country that is rare earth, domestic organic cerium salt very lacks, can only dependence on import, even and abroad, the price of the organic cerium salt of every gram does not wait to tens of dollars at several dollars yet.Ubiquity the very high problem of cost.
Another kind ofly prepare CeO with sol-gel method
2The method of film is to utilize inorganic salt as precursor powder, is mixed with solution, films then, thermal treatment, obtains CeO
2Film, but present result of study does not show the CeO that can obtain biaxial texture in this way as yet
2Film.It is a kind of with CeO that Japanese Patent JP2003027003-A has reported
2And other oxide compound is dissolved in the technology of preparation multi anti reflection coating in the organic solvent by mixing.Patent JP11323796-A has mentioned a kind of technology of making wallpaper with colloidal cerium salt.
At Chinese patent, application number 02101818.4, publication number 1463287, the method of cerium oxide slurry and manufacturing base material, the proposition ammonium polyacrylate that the adding degree of neutralization differs from one another in oxidation-containing cerium particulate cerium oxide slurry is as tensio-active agent, and the total amount of polyacrylate that suitably adjusting adds, to reach the uneven film on the graduation base material accurately, and have good stability, without separating into two-layer, solidify or change viscosity without the flocculation deposition.
The nitrate of cerium and alcoxides salt prepares the YBCO coating conductor buffer layer as precursor powder research such as E.Celik etc. [IEEE Trans.Appl.Superconduct.Vol.9, No.2 June 1999].The precursor powder that is adopted comprises Ce (NO
3)
36H
2O, Ce (NH
4)
2(NO
3)
6, Ce (C
5H
7O
2)
3XH
2O, Ce (C
2H
3O
2)
31.5H
2O and C
2(C
2O
4)
39H
2O etc.These organic or inorganic salt are dissolved in the Virahol, and adopt Glacial acetic acid and nitric acid,, become as clear as crystal up to colloid stirring at room 60 to 120 minutes as catalyzer.After filming on the Ni base band, find that by X-ray diffraction studies all films do not show the desired epitaxial orientation that obtains, but present the powdery diffractometry random orientation, in addition, by the prepared CeO of scanning electron microscopic observation
2Film is found to have a large amount of crackles and bubble in the film, prepares CeO in this way
2The film buffer layer exists bigger deficiency and limitation.E.Celik etc. [Materials Science and Engineering B94 (2002) 176/180] have also studied with inorganic salt and have prepared CeO as precursor powder
2The cracking problem of film.This research Ce (NO
3)
36H
2O is as presoma, as catalyzer, as solvent, disposed 11 kinds of different colloidal sols with Virahol with acetic acid, and then on the Ni of biaxial texture base band by filming and thermal treatment prepares CeO
2Film.This studies show that no matter use any colloid, the CeO of preparation
2All exist a large amount of crackles and bubble in the film.Author's systematic study CeO
2The cracking of film and the relation of thermal treatment process, the conclusion that draws are that the content of cerium is high more, and sintering temperature is high more, and then cracking is serious more.From the stereoscan photograph that this research is showed, its CeO
2Film surface exists a large amount of crackles, and crack size is at tens more than the micron.As the buffer layer of YBCO coating conductor, generally all need good texture and surface, but the film that this research obtains is a random orientation, and exists a large amount of crackles, illustrate that these a series of colloids are not suitable for preparing the CeO of biaxial texture, densification
2Film.
Nilgun Ozer[Solar Energy Materials ﹠amp; Solar Cells 68 (2001) 391-400] studied on glass with cerium ammonium nitrate and nitric acid, quadrol, ethanol preparation CeO
2The technology of film wherein uses ethanol as solvent, and nitric acid is as catalyzer, and trolamine is as stablizer and properties-correcting agent, and it is the CeO of 200 nanometers that the also thermal treatment of filming on substrate of glass has then obtained thickness
2Film.This research is carried out under very low sintering temperature, the CeO that obtains
2Film is a random orientation.Studies show that the introducing of nitrate ion will make a large amount of bubble of generation in the film.From the stereoscan photograph that this research is delivered, CeO wherein
2The surface have bigger roughness, exist problems such as particle aggregation.
[vacuum science and technology such as Peng Dingmin, 18 (1998) 247] use ethanol as solvent cerous nitrate, in mother liquor, add people's methyl ethyl diketone (or ethylene glycol) then, the film that on silicon substrate, makes with desk-top sol evenning machine at last, found that, exist a large amount of tiny cracks in the film that makes, what join that colloidal sol that gluing method makes still obtains on the silicon single-crystal of (111) orientation is polycrystal film with this, and grain orientation is stochastic distribution.
Generally speaking, utilize the higher organic cerium salt of cost, be configured to colloid as precursor powder, again by film, thermal treatment, the general CeO that all easily obtains to have excellent surface and biaxial texture
2Film; But utilize the colloidal sol of inorganic salt as precursor powder configuration, present progress shows as yet can obtain surface preferably, can form biaxial texture having on the substrate of orientation again.
Summary of the invention
The present invention is directed at present both at home and abroad at preparation CeO
2During film adopt organic cerium salt cost height more, perhaps utilize inorganic cerium salt but can not prepare densification, even, smooth, film, propose a kind ofly to prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method with biaxial texture
2Thin-film technique; Specific embodiment is:
1. the pre-treatment of precursor powder inorganic salt and organic solvent
1) preparation of soluble inorganic salt raw material and pre-treatment:, remove the hydroxyl that is adsorbed on the inorganic salt by the cryogenic vacuum processed;
2) preparation of organic solvent and pre-treatment: organic solvent can be divided into three major types: sequestrant, promoting agent and solvent; The purity of organic solvent generally is chemical pure or analytical pure, before use or in using by distillation, reflux or with other substance reaction and filter and dewater.
2.CeO
2The precursor aqueous solution preparation: anhydrous inorganic cerium salt is joined in sequestrant, promoting agent or the solvent, and the shared weight ratio of each component is: inorganic cerium salt 0.01~40%, sequestrant 1~40%, promoting agent 2~70%, solvent or stablizer 1~90%; With the vlil after the dissolving, temperature is 40~150 ℃, leaves standstill 1~24 hour, filters usefulness to be filmed.
3.CeO
2The preparation of film
1) adopt spin coating, dip-coating or spray-drying process to apply film forming at substrate surface, spin-coating method: 1000 rev/mins~6000 rev/mins of the speed of spin coating, 6 seconds~3 minutes spin coating time; During dip-coating, substrate is 3 seconds~1 minute residence time in colloidal sol, and pull rate is 10~150 mm/min;
2) will apply the substrate of film at Ar-4%H
2Heat in atmosphere or the air, temperature is from 60 ℃~500 ℃, and the time was carried out pyrolysis from 30 seconds~24 hours, to remove the organic solvent in the film.
3) sintering thermal treatment.Film after the pyrolysis is warmed up to 500 ℃~1200 ℃ with 1~200 ℃/minute speed, be incubated 3 minutes~120 hours, after sintering finishes in the atmosphere of oxidisability or reducing atmosphere, by the cooling of 2 ℃~200 ℃/minute speed, can obtain having biaxial texture, even compact, thickness is tens nanometers to several microns CeO
2Film.
Described metal or ceramic substrate material comprise: annealed state Ni and Ni alloy, annealed state Cu and Cu alloy, Ag and Ag alloy, yttria-stabilized zirconia (YSZ), strontium titanate, lanthanum aluminate, yttrium oxide, magnesium oxide, strontium titanate lanthanum (LSAT), gallic acid neodymium, strontium aluminate lanthanum, gallic acid strontium lanthanum or aluminic acid neodymium calcium.
Described inorganic salt are the inorganic cerium salt that contains crystal water or do not contain crystal water: cerous nitrate, cerium ammonium nitrate, Cerium II Chloride, cerous sulfate or ammonium sulfate cerium.
The invention has the beneficial effects as follows that (1) select for use inorganic cerium salt to prepare colloidal sol as precursor powder, replace the organic cerium salt that extensively adopts at present, reduced cost, and collosol stability is good, film forming properties is good; (2) introduce vacuum drying process, remove crystal water, avoid in follow-up joining in the glue process, hydroxyl is adsorbed on the cerium ion surface, hinders the bonding of coordinate bond; (3) add sequestrant, promoting agent or solvent after, can promote the chelating of cerium ion to improve the colloid quality by reflux; (4) do not introduce acid ion and hydroxide ion in the whole technological process, can reduce and form hole and defective in the film heat treatment process.(5) colloidal sol of this patent preparation and metal or ceramic bases all have good wetting property, can be at multiple metal or ceramic surface plated film, and can adjust the thickness and the grain size of film according to the practical application needs; According to the subsequent technique difference, can be formed with the texture film of specific orientation, also can form the film of no specific orientation.Have surface of good pattern and good biaxial texture simultaneously.(6) CeO
2Film can directly use, also can be at CeO
2Continue the deposition subsequent thin film above the film.
Description of drawings
The CeO of Fig. 1 on YSZ single-crystal, preparing
2The X ray diffracting spectrum of film.
The CeO of Fig. 2 on annealed state Ni base band, preparing
2The stereoscan photograph of film.
The CeO of Fig. 3 on annealed state Ni base band, preparing
2The X ray diffracting spectrum of film.
The CeO of Fig. 4 on annealed state Ni base band, preparing
2The X ray Phi scintigram of film.
The CeO of Fig. 5 on annealed state Ni base band, preparing
2The X ray Omega scintigram of film.
Embodiment
The present invention is directed at present both at home and abroad at preparation CeO
2During film adopt organic cerium salt cost height or utilize inorganic cerium salt but can not prepare densification, even, smooth, problems such as film, propose a kind ofly to prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method with biaxial texture
2Thin-film technique.Specific embodiment is:
1. the pre-treatment of precursor powder inorganic salt and organic solvent
1) preparation of soluble inorganic salt raw material and pre-treatment.By the cryogenic vacuum processed, remove the hydroxyl that is adsorbed on the inorganic salt.
2) preparation of organic solvent and pre-treatment.Organic solvent can be divided into three major types: sequestrant, promoting agent and solvent.The purity of organic solvent generally is chemical pure or analytical pure, before use or in using by distillation, reflux or with other substance reaction and filter and dewater.
2.CeO
2The system of precursor aqueous solution: anhydrous inorganic cerium salt is joined in sequestrant, promoting agent or the solvent, and the shared weight ratio of each component is: inorganic cerium salt 0.01~40%, sequestrant 1~40%, promoting agent 2~70%, solvent or stablizer 1~90%; With the vlil after the dissolving, temperature range from 40~150 ℃ not, leave standstill, the time is not waited from 1 hour by 24 hours, filters usefulness to be filmed.
3.CeO
2The preparation of film
1) adopt spin coating, dip-coating or spray-drying process to apply film forming at substrate surface, spin-coating method: with the speed of spin coating from 1000 rev/mins~6000 rev/mins, 6 seconds~3 minutes spin coating time; During dip-coating, substrate is 3 seconds~1 minute residence time in colloidal sol, and pull rate is 10~150 mm/min;
2) will apply the substrate of film at Ar-4%H
2Heat in atmosphere or the air, temperature is from 60 ℃~500 ℃, and the time was carried out pyrolysis from 30 seconds~24 hours, to remove the organic solvent in the film.
3) sintering thermal treatment.Film after the pyrolysis is warmed up to 500 ℃~1200 ℃ with 1~200 ℃/minute speed, be incubated 3 minutes~120 hours, after sintering finishes in the atmosphere of oxidisability or reducing atmosphere, by the cooling of 2 ℃~200 ℃/minute speed, can obtain having biaxial texture, even compact, thickness is tens nanometers to several microns CeO
2Film.
Above-mentioned metal or ceramic substrate material comprise: annealed state Ni and Ni alloy, annealed state Cu and Cu alloy, Ag and Ag alloy, yttria-stabilized zirconia (YSZ), strontium titanate, lanthanum aluminate, yttrium oxide, magnesium oxide, strontium titanate lanthanum (LSAT), gallic acid neodymium, strontium aluminate lanthanum, gallic acid strontium lanthanum or aluminic acid neodymium calcium.
Below by embodiment the present invention is specifically described.
Embodiment 1
Get six water cerous nitrate [Ce (NO
3)
36H
2O] 4.34 grams, 60 ℃ of vacuum-dryings 24 hours.Add anhydrous methyl ethyl diketone 6 grams, add zeolite, refluxed 24 hours, add anhydrous ethylene glycol monomethyl ether then at 100 ℃, make cubic capacity to 40 milliliter, refluxed 24 hours, add anhydrous methanol at last, refluxed 24 hours, and filter, add methyl alcohol again, make total collosol concentration reach 0.25 mol.Above-mentioned colloidal sol filtration, sealing and standing more than 48 hours, promptly be can be used to film.Film with spin-coating method on YSZ single-crystal with above-mentioned colloidal sol, get rid of the film parameter and be 1000rpm * 6 second+6000rpm * 30 second.Prepared gel-film was placed on 400 degrees centigrade the hot platform oven dry 10 minutes, then the film after the pyrolysis is placed the syllogic tube furnace, heat-up rate was 10 ℃/minute, 1000 ℃ of thermal treatments 1 hour, stove is cold then, and the atmosphere in the whole heat treatment process is air.Fig. 1 shows is to film on the YSZ single-crystal and obtaining the X ray diffracting spectrum of film, demonstration intensive (001) preferred orientation after 1 hour in 1000 ℃ of insulations with this colloidal sol.
Embodiment 2
Step of preparation process is identical with embodiment 1, and different is in the film preparation process, to adopt dip coating to replace spin-coating method to film.The technological process of dip coating is, the solution of preparation is taken advantage of and is placed in the beaker for about 50 milliliter, clamp the substrate that cleaned with the dop of dip coater, slowly immerse in the solution, after leaving standstill for 10 seconds, lift out from solution with the speed of 1 mm/second at the uniform velocity, carry out pyrolysis, thermal treatment then, its technology and embodiment 1 are identical.Obtain the thick CeO of about 100nm
2Film.
Embodiment 3
Get cerium ammonium nitrate [Ce (NH
4)
2(NO
3)
6] 10.96 grams.Add anhydrous methyl ethyl diketone 12 grams, add zeolite, refluxed 24 hours, add anhydrous ethylene glycol monomethyl ether then at 100 ℃, make cubic capacity to 80 milliliter, refluxed 24 hours, add anhydrous methanol at last, refluxed 24 hours, and filter, add methyl alcohol again, make total collosol concentration reach 0.1 mol.Above-mentioned colloidal sol filtration, sealing and standing more than 48 hours, promptly be can be used to film.Film with spin-coating method on the Ni of annealed state base band with above-mentioned colloidal sol, get rid of the film parameter and be 1000rpm * 6 second+4000rpm * 30 second.Prepared gel-film was placed on 350 degrees centigrade the hot platform oven dry 10 minutes, then the film after the pyrolysis is placed the syllogic tube furnace, heat-up rate was 25 ℃/minute, 950 ℃ of thermal treatments 1 hour, stove is cold then, and the atmosphere in the whole heat treatment process is Ar-4%H
2Fig. 2 shows is with film on the Ni of the annealed state base band stereoscan photograph of the even even curface that obtains of this colloidal sol.What Fig. 3 showed is to film on the Ni base band with this colloidal sol to obtain the X ray diffracting spectrum of film, demonstrate pure (001) orientation, what Fig. 4 showed is the X ray Phi scanning spectra of filming on the Ni base band and obtaining film with this colloidal sol, demonstrates good biaxial texture.What Fig. 5 showed is the X ray Omega scanning spectra of filming on the Ni base band and obtaining film with this colloidal sol, demonstrates good biaxial texture.
By the theoretical and experimental study over 3 years, we have successfully used this method, have prepared the CeO with biaxial texture at metal and ceramic surface
2Film, the ω of its texture and φ scanning result near in addition surpassed the organic cerium salt of external usefulness epitaxially grown CeO on metal base
2The result.The CeO that on the Ni base band, grows in this way
2Film, its X-ray diffraction has demonstrated good biaxial texture, Δ ω<5.5 °, Δ φ<6 °.By scanning electron microscope and AFM analysis revealed, film has the surface of good planeness, and its square root of the variance roughness is less than 10nm.
Claims (3)
1. one kind prepares biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Thin-film technique; It is characterized in that: prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method
2The specific embodiment of film is:
(1) pre-treatment of precursor powder inorganic salt and organic solvent
1) preparation of soluble inorganic salt raw material and pre-treatment:, remove the hydroxyl that is adsorbed on the inorganic salt by the cryogenic vacuum processed;
2) preparation of organic solvent and pre-treatment: organic solvent can be divided into three major types: sequestrant, promoting agent and solvent; The purity of organic solvent generally is chemical pure or analytical pure, before use or in using by distillation, reflux or with other substance reaction and filter and dewater;
(2) CeO
2The system of precursor aqueous solution: anhydrous inorganic cerium salt is joined in sequestrant, promoting agent or the solvent, and the shared weight ratio of each component is: inorganic cerium salt 0.01~40%, sequestrant 1~40%, promoting agent 2~70%, solvent or stablizer 1~90%; With the vlil after the dissolving, 40~150 ℃ of temperature, time of repose 1 hour~24 hours filters usefulness to be filmed;
(3) CeO
2The preparation of film
1) adopt spin coating, dip-coating or spray-drying process to apply film forming at substrate surface, spin-coating method: with the speed of spin coating from 1000 rev/mins~6000 rev/mins, 6 seconds~3 minutes spin coating time; During dip-coating, substrate is 3 seconds~1 minute residence time in colloidal sol, and pull rate is 10~150 mm/min;
2) substrate that will apply film is heated in Ar-4%H2 atmosphere or air, and temperature is from 60 ℃~500 ℃, and the time was carried out pyrolysis from 30 seconds~24 hours, to remove the organic solvent in the film;
3) sintering thermal treatment: the film after the pyrolysis is warmed up to 500 ℃~1200 ℃ with 1~200 ℃/minute speed, be incubated 3 minutes~120 hours, after sintering finishes in the atmosphere of oxidisability or reducing atmosphere, by the cooling of 2 ℃~200 ℃/minute speed, can obtain having biaxial texture, even compact, thickness is tens nanometers to several microns CeO
2Film.
2. prepare biaxial texture CeO according to claim 1 is described with the inorganic salt raw material liquid chemical method
2Thin-film technique; It is characterized in that: described metal or ceramic substrate material comprise: annealed state Ni and Ni alloy, annealed state Cu and Cu alloy, Ag and Ag alloy, yttria-stabilized zirconia (YSZ), strontium titanate, lanthanum aluminate, yttrium oxide, magnesium oxide, strontium titanate lanthanum (LSAT), gallic acid neodymium, strontium aluminate lanthanum, gallic acid strontium lanthanum or aluminic acid neodymium calcium.
3. prepare biaxial texture CeO according to claim 1 is described with the inorganic salt raw material liquid chemical method
2Thin-film technique; It is characterized in that: described inorganic salt are the inorganic cerium salt that contains crystal water or do not contain crystal water: cerous nitrate, cerium ammonium nitrate, Cerium II Chloride, cerous sulfate or ammonium sulfate cerium.
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