CN103008210B - Planarization method for high-temperature superconducting coated conductor substrate - Google Patents
Planarization method for high-temperature superconducting coated conductor substrate Download PDFInfo
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- CN103008210B CN103008210B CN201210532166.9A CN201210532166A CN103008210B CN 103008210 B CN103008210 B CN 103008210B CN 201210532166 A CN201210532166 A CN 201210532166A CN 103008210 B CN103008210 B CN 103008210B
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Abstract
The invention discloses a planarization method for a high-temperature superconducting coated conductor substrate, belonging to the technical field of preparation of a high-temperature superconducting material. The planarization method comprises the following steps of: (1) preparing anhydrous precursor solution, i.e., fully dissolving and uniformly mixing a silicon source and a solvent according to a predetermined proportion, adding ethanol, heating, stirring, distilling under low pressure to remove water, and fixing volume to form the anhydrous precursor solution; (2) coating first precursor solution on the surface of a substrate, performing spin coating, and annealing; and (3) uniformly coating second precursor solution on the substrate to form a solution film, performing spin coating and annealing to guarantee that the root mean square roughness of the surface of the thin film is less than 2 nm. An amorphous thin film prepared by the invention has not only an effect of leveling the substrate but also an effect of obstructing diffusion in a high-temperature superconducting coted conductor structure.
Description
Technical field
The invention belongs to high temperature superconducting materia preparing technical field, relate to the method for coating conductor texture base band liquid deposition planarization.
Background technology
Along with follow-on electronic product is towards development trend intelligent, integrated, hommization, the application of flexible substrate is more and more extensive, for example display screen, printed circuit board, advanced energy and material (as solar cell), and conductor of high-temperature superconductor coat (HTSCCs) etc.Compare with traditional material, flexible substrate has the advantages such as mechanical strength is high, volume is little, specific area is large, the more important thing is and adopts roller when prepared by roller (reel to reel) method for winding, can significantly reduce the cost that industry is manufactured; Yet the surface roughness of industrial flexible base band does not all reach the needed standard of equipment performance optimization that makes conventionally, like this its cheaply advantage just possibly cannot realize.
Conductor of high-temperature superconductor coat is one of the study hotspot in current superconduction field, and its preparation method comprises the auxiliary biaxial texture base band (RABiTS) of rolling and ion beam assisted depositing (IBAD).Adopt ion beam assisted depositing (IBAD) to obtain the substrate with highly textured growth of superconductive functional layer, the advantage that IBAD-MgO obtains texture fast with it is received very big concern.For reaching practical application, need the technique that a kind of energy is cheap, prepare fast the needed smooth substrate of IBAD-MgO.Traditional glossing is as smooth in machine glazed finish and electrochemical polish can make base band surface flatten.Machine glazed finish is a good method that obtains smooth base band, but because cost is high and efficiency is low, is not suitable for the preparation of long band or large-area coating; And electrochemical polish is only applicable to some specific astroloy material, be difficult to use on a large scale.
From traditional polishing mode, substrate surface is removed to one deck and reach that to reduce the object of roughness different, the coating conductor substrate preparation method of liquid deposition leveling adds at substrate surface the effect that one or more layers noncrystal membrane reaches planarization.At coarse substrate surface, apply one deck oxide precursor liquid, due to capillary effect, solution can be in the how residual part of sunk microcell, and few more residual at protruding microcell, the relative substrate surface of liquid film plays planarization effect; Through Overheating Treatment, precursor liquid experience solvent evaporates and thermal decomposition, be converted into amorphous oxides, although volume is compared liquid film, shrinks to some extent, compares original substrate surface again, and surface roughness declines.By repeatedly applying and heat treatment, the surface roughness of substrate can be down to 1nm left and right, and for follow-up IBAD-MgO texture layer provides good smooth surface, amorphous layer can also be as the barrier layer that stops base band and superconducting layer counterdiffusion simultaneously.It is simple that the method has technique, and nonhazardous is with low cost, is applicable to heavy industrialization application, so the preparation of conductor of high-temperature superconductor coat is significant.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of effectively quick, cheap in the substrate planarization technology of rough surface, can be applied to large area substrates and long band.
The technical scheme that the present invention solve the technical problem employing is that conductor of high-temperature superconductor coat substrate flattening method, is characterized in that, comprises the steps:
(1) anhydrous precursor liquid preparation: silicon source is completely dissolved and mixed by predetermined ratio with solvent, add the methyl alcohol of solvent volume 1/3～1/2, and be heated to 40～50 ℃ of stirrings, low-pressure distillation dewaters; Then stop low-pressure distillation and heating, only stir; Finally, by adding solvent to carry out constant volume, form the first precursor aqueous solution, the Si ion molar concentration of the first precursor aqueous solution is 0.2-0.8mol/l; By adding solvent dilution the first precursor aqueous solution, obtain the second precursor aqueous solution, its Si ion molar concentration is 0.02-0.2mol/l; The ratio of silicon source and solvent can be calculated by the silicon ion concentration of precursor aqueous solution.Described silicon source is ethyl orthosilicate or positive silicic acid propyl ester, and described solvent is isopropyl alcohol, or ethanol, or ether;
(2) spin coating: the first precursor aqueous solution is dropped in to substrate surface, apply the even liquid film of one deck on substrate; Annealing: the substrate that is coated with liquid film is warming up to 450～550 ℃ of sintering from room temperature with the speed of 2～10 ℃/min, insulation 10～30min, atmosphere is air, is then naturally cooled to room temperature, obtains single layer oxide noncrystal membrane; Repeatedly repeat spin coating and annealing process, until film surface r.m.s. roughness is less than 5nm, be greater than 2nm, obtain Multi-layer amorphous film;
(3) spin coating: the second precursor aqueous solution in step (1) is spun on to the Multi-layer amorphous film surface that step (2) obtains; Annealing: from room temperature, with the speed of 2～10 ℃/min, be warming up to 450～550 ℃ of sintering, insulation 10～30min, atmosphere is air, is then naturally cooled to room temperature, obtains single layer oxide noncrystal membrane; Repeatedly repeat spin coating and annealing, make film surface r.m.s. roughness be less than 2nm.
In described step (2), substrate is Hastelloy substrate or stainless steel substrate or Al
2o
3ceramic substrate, surperficial r.m.s. roughness scope is 20～100nm.
In described step (2) and step (3), spin coating speed is 2000～4000rpm, and the time is 20～60s.
In described step (3), surperficial r.m.s. roughness rms adopts AFM (AFM) test to obtain.
Compared with prior art, the present invention has the following advantages:
(1) the present invention is simple without expensive plant equipment, technique, with low cost, is applicable to heavy industrialization application;
(2) be not subject to the impact of substrate shape, material, wide application;
(3) prepared amorphous layer film not only can play the effect of smooth substrate, can also in conductor of high-temperature superconductor coat structure, play a part to intercept diffusion;
(4) raw material are organic compound, after decomposition, can not produce pernicious gas, environmentally safe.
Than Y2O3 material, be easy to crystallization, Y
2o
3and Al
2o
3the precursor liquid of composite is easy to the shortcoming such as unstable that hydrolysis causes, SiO
2material easily forms amorphous phase, and the clean surface of its stable nucleating point peace lay the grain is very beneficial for IBAD-MgO film and obtains fast texture thereon, is for the ideal material of substrate planarization in IBAD route.
Accompanying drawing explanation
Fig. 1 is the SiO of example one
2x-ray diffraction θ-2 θ the scintigram of film.
Fig. 2 is AFM (AFM) figure of the Hastelloy substrate of example one, and Fig. 2 a is X-Y scheme, and Fig. 2 b is 3 dimensional drawing.
Fig. 3 is the SiO of example one
2the AFM figure of film, Fig. 3 a is X-Y scheme, Fig. 3 b is 3 dimensional drawing.
Fig. 4 is the SiO of example two
2the AFM figure of film, Fig. 4 a is X-Y scheme, Fig. 4 b is 3 dimensional drawing.
The specific embodiment
The invention provides chemical solution method and prepare SiO
2film, for the method for conductor of high-temperature superconductor coat substrate planarization, comprises the steps:
(1) anhydrous precursor liquid preparation: by silicon source and solvent in proportion under room temperature magnetic agitation completely dissolving mix, add the methyl alcohol of solvent volume 1/3-1/2, and be heated to 40～50 ℃ of magnetic agitation and carry out low-pressure distillation and dewater; Stop low-pressure distillation and heating, only stir; Finally, by adding solvent to carry out constant volume, form anhydrous precursor aqueous solution, i.e. the first precursor aqueous solution.The Si ion molar concentration of the first precursor aqueous solution is 0.2-0.8mol/l, by adding solvent dilution the first precursor aqueous solution, obtains the second precursor aqueous solution, and its Si ion molar concentration is 0.02-0.2mol/l;
(2) spin coating: the first precursor aqueous solution in step (1) is dropped in to substrate surface, use gyroscope to apply the even liquid film of one deck on substrate;
Annealing: the substrate that is coated with liquid film is placed in to pipe type sintering furnace, is warming up to 450～550 ℃ of insulation 10～30min from room temperature with the speed of 2～10 ℃/min, atmosphere is air, then allows stove naturally be cooled to room temperature, obtains single layer oxide noncrystal membrane.
Repeatedly repeat spin coating and annealing process, until film surface r.m.s. roughness (rms) is less than 5nm, be greater than 2nm, obtain Multi-layer amorphous film.
(3) spin coating: the second precursor aqueous solution in step (1) is dropped in to the Multi-layer amorphous film surface that step (2) obtains, use gyroscope to apply the even liquid film of one deck on substrate.Annealing: the substrate that is coated with liquid film is placed in to pipe type sintering furnace, is warming up to 450～550 ℃ of insulation 10～30min from room temperature with the speed of 2～10 ℃/min, atmosphere is air, then allows stove naturally be cooled to room temperature, obtains single layer oxide noncrystal membrane.Repeatedly repeat spin coating and annealing process, make film surface r.m.s. roughness be less than 2nm.
In described step (1), silicon source is ethyl orthosilicate or positive silicic acid propyl ester, and solvent is isopropyl alcohol or ethanol or ether.In step (1), in molar ratio, the ratio of silicon source and solvent can be silicon: solvent=0.3:1～1:1.
In described step (2), substrate is Hastelloy (Hastelloy) substrate or stainless steel substrate or Al
2o
3ceramic substrate, surperficial r.m.s. roughness scope is 20～100nm.
In described step (2) (3), spin coating speed is 2000～4000rpm, and the time is 20～60s.
In described step (3), surperficial r.m.s. roughness rms adopts AFM (AFM) test to obtain.
Embodiment is as follows more specifically:
Embodiment mono-: chemical solution method is prepared SiO
2film is for the method for conductor of high-temperature superconductor coat substrate planarization, and concrete implementation step is as follows:
(1) 6.24g ethyl orthosilicate is dissolved in 30ml isopropyl alcohol, under room temperature magnetic agitation, completely dissolve and mix, add 10ml methyl alcohol and be heated to 40～50 ℃ of magnetic agitation, carry out decompression distillation and dewater, finally add isopropyl alcohol and be settled to 50ml, the anhydrous SiO that preparation forms
2the first precursor aqueous solution, Si ion molar concentration is 0.6mol/l.
(2) get anhydrous SiO in step (1)
2precursor liquid 5ml, adds isopropanol solvent to dilute, and is settled to 50ml, the anhydrous SiO that preparation forms
2the second precursor aqueous solution, Si ion molar concentration is 0.06mol/l.
(3) the first precursor aqueous solution in step (1) is dropped in to Hastelloy (Hastelloy) substrate surface, adopt whirler to be evenly coated on substrate, spin coating speed is 2000rpm, time is 30s, the substrate that is coated with liquid film is placed in to pipe type sintering furnace, from room temperature, with the speed of 3 ℃/min, is warming up to 500 ℃ of insulation 15min, atmosphere is air, then allow stove naturally be cooled to room temperature, obtain single layer oxide noncrystal membrane.Repeat spin coating and annealing process 4 times, obtain 5 layers of noncrystal membrane.
(4) the second precursor aqueous solution in step (2) is dropped in to the Multi-layer amorphous film surface that step (3) obtains, adopt whirler to be evenly coated on substrate, spin coating speed is 3000rpm, time is 30s, the substrate that is coated with liquid film is placed in to pipe type sintering furnace, from room temperature, with the speed of 3 ℃/min, is warming up to 500 ℃ of insulation 15min, atmosphere is air, then allow stove naturally be cooled to room temperature, obtain single layer oxide noncrystal membrane.Repeat spin coating and annealing process 3 times, can make the sample of flat surface.
Fig. 1 is the SiO of example one preparation
2x-ray diffraction θ-2 θ the scintigram of film.There are three very faint diffraction maximums at 44.5 °, 51.8 ° and 75 ° in it, is 111,200 and 220 diffraction maximums of substrate Ni, without SiO
2diffraction maximum exists, and shows SiO
2for amorphous state.
Fig. 2 is AFM (AFM) the two and three dimensions stereogram of the Hastelloy substrate of example one, its rough surface, and r.m.s. roughness (rms) is 26.3nm.
Fig. 3 is the SiO of example one preparation
2the AFM two and three dimensions stereogram of film, rms is 1.36nm, the surface roughness of comparing Hastelloy substrate has reduced by one more than the order of magnitude.
Embodiment bis-: chemical solution method is prepared SiO
2film is for the method for conductor of high-temperature superconductor coat substrate planarization, and concrete implementation step is as follows:
(1) 1.04g ethyl orthosilicate is dissolved in 10ml isopropyl alcohol, under room temperature magnetic agitation, completely dissolve and mix, add 5ml methyl alcohol and be heated to 40～50 ℃ of magnetic agitation, carry out decompression distillation and dewater, finally add isopropyl alcohol and be settled to 20ml, the anhydrous SiO that preparation forms
2the first precursor aqueous solution, Si ion molar concentration is 0.25mol/l.
(2) get anhydrous SiO in step (1)
2precursor liquid 4ml, adds isopropanol solvent to dilute, and is settled to 50ml, the anhydrous SiO that preparation forms
2the second precursor aqueous solution, Si ion molar concentration is 0.02mol/l.
(3) the first precursor aqueous solution in step (1) is dropped in to Hastelloy (Hastelloy) substrate surface, adopt whirler to be evenly coated on substrate, spin coating speed is 3000rpm, time is 30s, the substrate that is coated with liquid film is placed in to pipe type sintering furnace, from room temperature, with the speed of 2 ℃/min, is warming up to 450 ℃ of insulation 20min, atmosphere is air, then allow stove naturally be cooled to room temperature, obtain single layer oxide noncrystal membrane.Repeat spin coating and annealing process 14 times, obtain 15 layers of noncrystal membrane.
(4) the second precursor aqueous solution in step (2) is dropped in to the Multi-layer amorphous film surface that step (3) obtains, adopt whirler to be evenly coated on substrate, spin coating speed is 3000rpm, time is 30s, the substrate that is coated with liquid film is placed in to pipe type sintering furnace, from room temperature, with the speed of 2 ℃/min, is warming up to 450 ℃ of insulation 20min, atmosphere is air, then allow stove naturally be cooled to room temperature, obtain single layer oxide noncrystal membrane.Repeat spin coating and annealing process 9 times, can make the sample of flat surface.
Fig. 4 is the SiO of example two preparations
2the AFM two and three dimensions stereogram of film, rms is 1.15nm.
Claims (3)
1. conductor of high-temperature superconductor coat substrate flattening method, is characterized in that, comprises the steps:
(1) anhydrous precursor liquid preparation: silicon source is completely dissolved and mixed by predetermined ratio with solvent, add the methyl alcohol of solvent volume 1/3～1/2, and be heated to 40～50 ℃ of stirrings, low-pressure distillation dewaters; Then stop low-pressure distillation and heating, only stir; Finally, by adding solvent to carry out constant volume, form the first precursor aqueous solution, the Si ion molar concentration of the first precursor aqueous solution is 0.2-0.8mol/l; By adding solvent dilution the first precursor aqueous solution, obtain the second precursor aqueous solution, its Si ion molar concentration is 0.02-0.2mol/l;
Described silicon source is ethyl orthosilicate or positive silicic acid propyl ester, and described solvent is isopropyl alcohol, or ethanol, or ether;
(2) spin coating: the first precursor aqueous solution is dropped in to substrate surface, apply the even liquid film of one deck on substrate; Annealing: the substrate that is coated with liquid film is warming up to 450～550 ℃ of sintering from room temperature with the speed of 2～10 ℃/min, insulation 10～30min, atmosphere is air, is then naturally cooled to room temperature, obtains single layer oxide noncrystal membrane; Repeatedly repeat spin coating and annealing process, until film surface r.m.s. roughness is less than 5nm, be greater than 2nm, obtain Multi-layer amorphous film;
(3) spin coating: the second precursor aqueous solution in step (1) is spun on to the Multi-layer amorphous film surface that step (2) obtains; Annealing: from room temperature, with the speed of 2～10 ℃/min, be warming up to 450～550 ℃ of sintering, insulation 10～30min, atmosphere is air, is then naturally cooled to room temperature, obtains single layer oxide noncrystal membrane; Repeatedly repeat spin coating and annealing, make film surface r.m.s. roughness be less than 2nm.
2. conductor of high-temperature superconductor coat substrate flattening method as claimed in claim 1, is characterized in that, in described step (2), substrate is Hastelloy substrate or stainless steel substrate or Al
2o
3ceramic substrate, surperficial r.m.s. roughness scope is 20～100nm.
3. conductor of high-temperature superconductor coat substrate flattening method as claimed in claim 1, is characterized in that, in described step (2) and step (3), spin coating speed is 2000～4000rpm, and the time is 20～60s.
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| JPS62170108A (en) * | 1986-01-22 | 1987-07-27 | 鹿児島大学長 | Super conductor containing nb, si and al and oxide thereof having transition temperature 77k or more |
| US6251835B1 (en) * | 1997-05-08 | 2001-06-26 | Epion Corporation | Surface planarization of high temperature superconductors |
| WO2003082482A1 (en) * | 2002-03-25 | 2003-10-09 | Penn State Research Foundation | Method for producing boride thin films |
| US7718574B2 (en) * | 2004-04-08 | 2010-05-18 | Superpower, Inc. | Biaxially-textured film deposition for superconductor coated tapes |
| CN101178955B (en) * | 2007-10-26 | 2010-06-30 | 上海大学 | Method for enhancing CeO2 thin film thickness for coatings conductive body |
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