CN100347336C - 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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- CN100347336C CN100347336C CNB2004100426246A CN200410042624A CN100347336C CN 100347336 C CN100347336 C CN 100347336C CN B2004100426246 A CNB2004100426246 A CN B2004100426246A CN 200410042624 A CN200410042624 A CN 200410042624A CN 100347336 C CN100347336 C CN 100347336C
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Abstract
The present invention discloses a process for preparing biaxial-texture CeO2 films by an inorganic salt material liquid phase chemical method, which belongs to the technical range of the preparation of superconducting film materials. Firstly, the dehydration pretreatment of inorganic salt and organic solvent is carried out, coating liquid is prepared, a CeO2 film is coated on a substrate, and the biaxial-texture CeO2 film is obtained through pyrolysis and sintering. With favorable lattice matching performance, favorable chemical stability and favorable capacity for preventing oxygen from diffusing, the biaxial-texture CeO2 film is a good buffer layer material, and can be applied to the field of superconducting coating layer conductors, fuel cells, catalyst and optics. The present invention can be used for preparing CeO2 films with national abundant inorganic salt resources and developing functional films.
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: describedly prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Film is with CeO
2Colloidal sol adopts spin-coating method to apply into CeO on substrate surface
2Film, concrete technology is as follows:
Get inorganic salt raw material 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 at 100 ℃, add anhydrous ethylene glycol monomethyl ether then, make cubic capacity to 40 milliliter, refluxed 24 hours, add anhydrous methanol, refluxed 24 hours, and filter, add methyl alcohol again, make total collosol concentration reach 0.25 mol, above-mentioned colloidal sol is filtered, sealing and standing is filmed with spin-coating method on the yttria-stabilized zirconia YSZ single-crystal more than 48 hours then, 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, and then the film after the pyrolysis placed in the syllogic tube furnace, in air, heat up with 10 ℃/minute heat-up rates, 1000 ℃ of thermal treatments 1 hour, treat that stove obtains the biaxial texture CeO of (001) preferred orientation after cold
2Film.
2. one kind prepares biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Thin-film technique; It is characterized in that: describedly prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Film is with CeO
2Colloidal sol adopts spin-coating method to apply into CeO on substrate surface
2Film, concrete technology is as follows:
Get inorganic salt raw material 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 at 100 ℃, add anhydrous ethylene glycol monomethyl ether then, make cubic capacity to 80 milliliter, refluxed 24 hours, add anhydrous methanol, refluxed 24 hours, and filter, add methyl alcohol again, make total collosol concentration reach 0.1 mol, above-mentioned colloidal sol is filtered, sealing and standing was filmed with spin-coating method on the Ni of annealed state base band more than 48 hours, 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, and then the film after the pyrolysis placed the syllogic tube furnace, whole heat treatment process is at Ar-4%H
2Under the atmosphere, heat up,, treat that stove obtains the biaxial texture CeO of (001) preferred orientation after cold 950 ℃ of thermal treatments 1 hour with 25 ℃/minute heat-up rates
2Film.
3. one kind prepares biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Thin-film technique; It is characterized in that: describedly prepare biaxial texture CeO with the inorganic salt raw material liquid chemical method
2Film is with CeO
2Colloidal sol adopts dip coating to prepare CeO on substrate surface
2Film, concrete technology is as follows:
Get inorganic salt raw material 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 at 100 ℃, add anhydrous ethylene glycol monomethyl ether then, make cubic capacity to 40 milliliter, refluxed 24 hours, add anhydrous methanol, refluxed 24 hours, and filter, add methyl alcohol again, make total collosol concentration reach 0.25 mol, above-mentioned colloidal sol is filtered, sealing and standing is more than 48 hours, the colloidal sol of preparation taken advantage of for 50 milliliters be placed in the beaker, clamps the yttria-stabilized zirconia YSZ substrate that cleaned with the dop of dip coater, slowly immerse in the colloidal sol, after leaving standstill for 10 seconds, from colloidal sol, lift out, prepared gel-film was placed on 400 degrees centigrade the hot platform oven dry 10 minutes with the speed of 1 mm/second at the uniform velocity, then the film after the pyrolysis is placed in the syllogic tube furnace, in air, heat up with 10 ℃/minute heat-up rates,, treat that stove obtains the thick biaxial texture CeO of 100nm after cold 1000 ℃ of thermal treatments 1 hour
2Film.
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| CN100458981C (en) * | 2006-10-09 | 2009-02-04 | 西南交通大学 | Method for preparing buffer layer of conductor of high-temperature superconductor coat |
| CN101188152B (en) * | 2007-10-26 | 2010-08-11 | 上海大学 | Making method of CeO2 film for coated layer conductor |
| CN102677030A (en) * | 2011-11-02 | 2012-09-19 | 西南交通大学 | Method for preparing high-temperature superconducting coating conductor CeO2 buffer layer film on biaxial texture NiW alloy substrate |
| CN102864444A (en) * | 2012-09-03 | 2013-01-09 | 西南交通大学 | Method for improving critical thickness of CeO2 film prepared with chemical solution method |
| CN105002479A (en) * | 2015-07-13 | 2015-10-28 | 西安理工大学 | Buffer layer for high-temperature superconducting coated conductor and preparation method of buffer layer |
| CN110863191B (en) * | 2019-11-27 | 2021-06-04 | 东北大学 | Metal matrix with coating and preparation method thereof |
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| US6077344A (en) * | 1997-09-02 | 2000-06-20 | Lockheed Martin Energy Research Corporation | Sol-gel deposition of buffer layers on biaxially textured metal substances |
| US6673387B1 (en) * | 2000-07-14 | 2004-01-06 | American Superconductor Corporation | Control of oxide layer reaction rates |
| CN1494168A (en) * | 2002-10-28 | 2004-05-05 | 北京有色金属研究总院 | Method of preparing buttering using inorganic salt as precusor |
-
2004
- 2004-05-28 CN CNB2004100426246A patent/CN100347336C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077344A (en) * | 1997-09-02 | 2000-06-20 | Lockheed Martin Energy Research Corporation | Sol-gel deposition of buffer layers on biaxially textured metal substances |
| US6673387B1 (en) * | 2000-07-14 | 2004-01-06 | American Superconductor Corporation | Control of oxide layer reaction rates |
| CN1494168A (en) * | 2002-10-28 | 2004-05-05 | 北京有色金属研究总院 | Method of preparing buttering using inorganic salt as precusor |
Non-Patent Citations (1)
| Title |
|---|
| 在SrTiO3基底上用溶胶-凝胶法制备CeO2缓冲层 杨良斌等.低温物理学报，第25卷 2003 * |
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