US4920093A
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Fabrication of superconducting oxide thin films by sol-gel method
Assignee: Toray Industries Inc
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Filing: 1988-05-26
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Granted: 1990-04-24
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Expires: 2008-05-26
Abstract
Abstract A solution for forming a superconductive thin film prepared by dissolving a mol of a compound selected from group A consisting of alkoxides and alkoxyalkoxides of a rare earth metal element; b mol of a compound selected from group B consisting of alkoxides and alkoxyalkoxides of Ba, Sr and Ca; and c mol of a compound selected from group C consisting of alkoxides and alkoxyalkoxides of Cu in e liter of a compound selected from group E, a solvent selected from alcohols together with d mol of a compound selected from group D having hydrolysis inhibitory action such as an amine, a ketone and a glycol, such that the following relationships: 0.1×(a+b+c)≧d≧3×(a+b+c) and 0.1≧[(a+b+c)/e]≧e may be satisfied. A superconductive thin film having homogeneous composition, uniform film thickness and excellent superconductive propertied, free from contaminants and cracking, is produced by forming a thin film using the solution on a heat-resistant substrate and calcining the thus formed thin film as carried on the substrate.
Inventors
- 👤 Toshihisa Nonaka
- 👤 Keisuke Kobayashi
- 👤 Hiroyuki Igaki
- 👤 Michiyasu Matsuki
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 22:51
CPC Classifications
C; C04; C04B; C04B41/00; C04B41/009; C03; C03C; C03C17/00; C03C17/22; C03C17/23; C03C17/25; C04B35/00; C04B35/01; C04B35/45; C04B35/4504; C04B41/45; C04B41/50; C04B41/5025; C04B41/80; C04B41/81; C04B41/85; C04B41/87; H; H10; H10N; H10N60/00; H10N60/01; H10N60/0268; H10N60/0296; H10N60/0324; C03C2217/00; C03C2217/20; C03C2217/21; C03C2217/229; C03C2217/23; C03C2218/00; C03C2218/10; C03C2218/11; C03C2218/113; Y; Y10; Y10S; Y10S505/00; Y10S505/725; Y10S505/734; Y10S505/735
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
216 words
A method of forming a superconductive thin film comprising: a step of preparing a solution containing an amount (a) of mols of at least one compound selected from the group A consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of La; an amount (b) of mols at least one compound selected from the group B consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of a metal selected from Ba, Sr and Ca; an amount (c) of mols of at least one compound selected from the group C consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of Cu; an amount (d) of mols for inhibiting hydrolysis of at least one compound selected from the group D consisting of monoethanolamine, diethanolamine, triethanolamine, mono-2-propanolamine, di-2-propanolamine, acetylacetone, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; and an amount (e) of liters of at least one compound selected from the group E consisting of methanol, ethanol, propanol, butanol, methoxyethanol and ethoxyethanol; said amounts (a)-(e) satisfying the following equations: 0.1×(a+b+c)≦d≦3×(a+b+c) and 0.01≦{(a+b+c)/e}≦3; a step of forming a thin film of the solution as prepared above on a heat-resistant substrate; a step of drying the film thus formed; and a step of calcining said film in an oxidative atmosphere at 350° to 1,150° C. to make said film superconductive.
Claim 2
Independent Claim
216 words
A method of forming a superconductive thin film comprising: a step of preparing a solution containing an amount (a) of mols of at least one compound selected from the group A consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of La; an amount (b) of mols at least one compound selected from the group B consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of a metal selected from Ba, Sr and Ca; an amount (c) of mols of at least one compound selected from the group C consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of Cu; an amount (d) of mols for inhibiting hydrolysis of at least one compound selected from the group D consisting of monoethanolamine, diethanolamine, triethanolamine, mono-2-propanolamine, di-2-propanolamine, acetylacetone, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; and an amount (e) of liters of at least one compound selected from the group E consisting of methanol, ethanol, propanol, butanol, methoxyethanol and ethoxyethanol; said amounts (a)-(e) satisfying the following equations: 0.1×(a+b+c)≦d≦3×(a+b+c) and 0.01≦{(a+b+c)/e}≦3; a step of forming a thin film of the solution as prepared above on a heat-resistant substrate; a step of drying the film thus formed; and a step of calcining said film in an oxidative atmosphere at 350° to 1,150° C. to make said film superconductive.
Claim 3
Dependent Claim
23 words
The method according to claim 1, wherein said compounds selected from the groups D and E are preliminarily subjected to dehydration treatment, respectively.
Claim 4
Dependent Claim
16 words
The method according to claim 1, wherein said solution satisfies the following relationships: 0.5×(a+b+c)≦d≦2×(a+b+c) and 0.1≦[(a+b+c)/e]≦1.
Claim 5
Dependent Claim
28 words
The method according to claim 3, wherein said solution further satisfies the following relationship: a:b:c=(2-x):x:y, wherein x and y are numerals satisfying the following relationships: 0<x≦0.3 and 0.9≦y≦1.1.
Claim 6
Dependent Claim
41 words
The method according to claim 1, wherein the operation of mixing said compound selected from the group A, said compound selected from the group B and said compound selected from the group C is carried out in a dry nitrogen atmosphere.
Claim 7
Dependent Claim
35 words
The method according to claim 1, wherein said heat-resistant substrate comprises any one selected from gold, silver and platinum or an alloy containing at least one of gold, silver and platinum as a major component.
Claim 8
Dependent Claim
13 words
The method according to claim 1, wherein said heat-resistant substrate comprises a glass.
Claim 9
Dependent Claim
49 words
The method according to claim 1, wherein said heat-resistant substrate comprises a ceramic selected from alumina, alumina silica, magnesia, partially stabilized zirconia, yttria stabilized zirconia, yttria, lanthania, silicon carbide, titanium carbide, silicon nitride, niobium nitride, boron nitride, alkali titanate, potassium lead silicate, strontium titanate, titanium boride and zirconium boride.
Claim 10
Dependent Claim
29 words
The method according to claim 1, wherein the thin film of the solution is formed by means of any of brush coating, roll coating, spray coating and dip coating.
Claim 11
Dependent Claim
26 words
The method according to claim 1, wherein the calcination is carried out in air or in an atmosphere where the oxygen concentration is 20 to 100%.
Claim 12
Independent Claim
231 words
A method of forming a superconductive thin film comprising: a step of preparing a solution containing an amount (a) of mols of at least one compound selected from the group A consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of a metal selected from Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu; an amount (b) of mols at least one compound selected from the group B consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of a metal selected from Ba and Sr; an amount (c) of mols of at least one compound selected from the group C consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of Cu; an amount (d) of mols for inhibiting hydrolysis of at least one compound selected from the group D consisting of monoethanolamine, diethanolamine, triethanolamine, mono-2-propanolamine, di-2-propanolamine, acetylacetone, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; and an amount (e) of liters of at least one compound selected from the group E consisting of methanol, ethanol, propanol, butanol, methoxyethanol and ethoxyethanol; said amounts (a)-(e) satisfying the following equations: 0.1×(a+b+c)≦d≦3×(a+b+c) and 0.01≦{(a+b+c)/e}≦3; a step of forming a thin film of the solution as prepared above on a heat-resistant substrate; a step of drying the film thus formed; and a step of calcining said film in an oxidative atmosphere at 350° to 1,100° C. to make said film superconductive.
Claim 13
Independent Claim
231 words
A method of forming a superconductive thin film comprising: a step of preparing a solution containing an amount (a) of mols of at least one compound selected from the group A consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of a metal selected from Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu; an amount (b) of mols at least one compound selected from the group B consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of a metal selected from Ba and Sr; an amount (c) of mols of at least one compound selected from the group C consisting of methoxide, ethoxide, propoxide, butoxide, methoxyethoxide and ethoxyethoxide of Cu; an amount (d) of mols for inhibiting hydrolysis of at least one compound selected from the group D consisting of monoethanolamine, diethanolamine, triethanolamine, mono-2-propanolamine, di-2-propanolamine, acetylacetone, ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; and an amount (e) of liters of at least one compound selected from the group E consisting of methanol, ethanol, propanol, butanol, methoxyethanol and ethoxyethanol; said amounts (a)-(e) satisfying the following equations: 0.1×(a+b+c)≦d≦3×(a+b+c) and 0.01≦{(a+b+c)/e}≦3; a step of forming a thin film of the solution as prepared above on a heat-resistant substrate; a step of drying the film thus formed; and a step of calcining said film in an oxidative atmosphere at 350° to 1,100° C. to make said film superconductive.
Claim 14
Dependent Claim
23 words
The method according to claim 11, wherein said compounds selected from the groups D and E are preliminarily subjected to dehydration treatment, respectively.
Claim 15
Dependent Claim
16 words
The method according to claim 11, wherein said solution satisfies the following relationships: 0.5×(a+b+c)≦d≦2×(a+b+c) and 0.1≦[(a+b+c)/e]≦1.
Claim 16
Dependent Claim
28 words
The method according to claim 13, wherein said solution further satisfies the following relationship: a:b:c=(1±x):(2±y):3, wherein x and y are numerals satisfying the following relationships: 0≦x≦0.1 and 0≦y≦0.1.
Claim 17
Dependent Claim
41 words
The method according to claim 11, wherein the operation of mixing said compound selected from the group A, said compound selected from the group B and said compound selected from the group C is carried out in a dry nitrogen atmosphere.
Claim 18
Dependent Claim
34 words
The method according to claim 11, wherein said heat-resistant substrate comprises any one of gold, silver and platinum or an alloy containing at least one of gold, silver and platinum as a major component.
Claim 19
Dependent Claim
13 words
The method according to claim 11, wherein said heat-resistant substrate comprises a glass.
Claim 20
Dependent Claim
49 words
The method according to claim 11, wherein said heat-resistant substrate comprises a ceramic selected from alumina, alumina silica, magnesia, partially stabilized zirconia, yttria stabilized zirconia, yttria, lanthania, silicon carbide, titanium carbide, silicon nitride, niobium nitride, boron nitride, alkali titanate, potassium lead silicate, strontium titanate, titanium boride and zirconium boride.
Claim 21
Dependent Claim
29 words
The method according to claim 11, wherein the thin film of the solution is formed by means of any of brush coating, roll coating, spray coating and dip coating.
Claim 22
Dependent Claim
26 words
The method according to claim 11, wherein the calcination is carried out in air or in an atmosphere where the oxygen concentration is 20 to 100%.
Claim 23
Dependent Claim
37 words
The method according to claim 11, further comprising a step of cooling said thin film after calcination, wherein the cooling from 500° C. to room temperature is carried out at a rate of 0.1° to 2° C./min.
Claim 24
Dependent Claim
38 words
The method according to claim 11, further comprising a step of cooling said thin film after calcination, and a step of heat-treating said film in an oxidative atmosphere at 300° to 700° C. for 10 hours or more.
Claim 25
Dependent Claim
16 words
The method according to claim 2, wherein said solution satisfies the following relationship: 0.5×(a+b+c)≦d≦2×(a+b+c) and 0.1≦{(a+b+c)/e}≦1.
Claim 26
Dependent Claim
28 words
The method according to claim 23, wherein said solution further satisfies the following relationships: a:b:c=(2-x):x:y, wherein x and y are numerals satisfying the following relationships: 0<x≦0.3 and 0.9≦y≦1.1.
Claim 27
Dependent Claim
41 words
The method according to claim 24, wherein the operation of mixing said compound selected from the group A, said compound selected from the group B and said compound selected from the group C is carried out in a dry nitrogen atmosphere.
Claim 28
Dependent Claim
26 words
The method according to claim 25, wherein the calcination is carried out in air or in an atmosphere where the oxygen concentration is 20 to 100%.
Claim 29
Dependent Claim
16 words
The method according to claim 12, wherein said solution satisfies the following relationships: 0.5×(a+b+c)≦d≦2×(a+b+c) and 0.1≦{(a+b+c)/e}≦1.
Claim 30
Dependent Claim
28 words
The method according to claim 27, wherein said solution further satisfies the following relationship: a:b:c=(1±x):(2±y):3, wherein x and y are numerals satisfying the following relationships: 0≦x≦0.1 and 0≦y≦0.1.
Claim 31
Dependent Claim
41 words
The method according to claim 28, wherein the operation of mixing said compound selected from the group A, said compound selected from the group B and said compound selected from the group C is carried out in a dry nitrogen atmosphere.
Claim 32
Dependent Claim
26 words
The method according to claim 29, wherein the calcination is carried out in air or in an atmosphere where the oxygen concentration is 20 to 100%.
Claim 33
Dependent Claim
37 words
The method according to claim 30, further comprising a step of cooling said thin film after calcination, wherein the cooling from 500° C. to room temperature is carried out at a rate of 0.1° to 2° C./min.
Claim 34
Dependent Claim
38 words
The method according to claim 30, further comprising a step of cooling said thin film after calcination, and a step of heat-treating said film in an oxidative atmosphere at 300° to 700° C. for 10 hours or more.
References Cited (Backward Citations)
US4614673A
Cited
US4636440A
Cited
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