CN106486205A - A kind of SrTiO3With LaAlO3The preparation method of double nano granule doped YBCO laminated film - Google Patents

A kind of SrTiO3With LaAlO3The preparation method of double nano granule doped YBCO laminated film Download PDF

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CN106486205A
CN106486205A CN201610875912.2A CN201610875912A CN106486205A CN 106486205 A CN106486205 A CN 106486205A CN 201610875912 A CN201610875912 A CN 201610875912A CN 106486205 A CN106486205 A CN 106486205A
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precursor liquid
ybco
absolute methanol
atmosphere
doping
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CN106486205B (en
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索红莉
王田田
徐燕
仪宁
李春燕
马麟
刘敏
王毅
孙硕
田民
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Beijing University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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Abstract

A kind of SrTiO3With LaAlO3The preparation method of double nano granule doped YBCO laminated film, its step is as follows：Precursor liquid is spun in substrate, obtains the precursor film being attached to substrate surface, precursor film is placed in the quartz tube furnace being passed through dry oxygen, is raised to 150 DEG C with the speed of 10 DEG C/min at room temperature；It is raised to 400 DEG C with the speed of 1.5～3 DEG C/min again, and is incubated 10min, when temperature is higher than 150 DEG C, the oxygen being dried is changed into the oxygen of humidity, moisture content is 3.1%；Then rise to 770～840 DEG C with the speed of 5 DEG C/min again, be incubated 2～3h；Wherein, in 400 DEG C to 500 DEG C temperature-rise periods, atmosphere is dry Ar/O2Atmosphere；When rising to 550 DEG C, atmosphere is changed to the Ar/O of humidity2；Dampness is gained dry Ar/O by the last 30min of insulation2Atmosphere；After insulation finishes, sample furnace cooling.The present invention solves the problems, such as that under externally-applied magnetic field, thin film pinning is limited, cannot continue to improve current capacity.

Description

A kind of SrTiO3With LaAlO3The preparation of double nano granule doped YBCO laminated film Method
Technical field
The invention belongs to high temperature superconducting materia preparing technical field is and in particular to a kind of double nano granule doped YBCO is combined The preparation method of thin film.
Background technology
In numerous superconductors, with yttrium barium copper oxide (YBa2Cu3O7, YBCO) be representative second filial generation high-temperature superconducting coating Conductor has high irreversibility field (7T) at liquid nitrogen temperature (77K), and high current capacity (can reach 107A/cm2), low friendship Stream loss and potential price advantage are it is considered to be there is the superconductor of application potential most.Superconductor is applied to necessarily mostly Under the conditions of externally-applied magnetic field, studies have shown that, ybco film its J under outer field actioncValue and externally-applied magnetic field have following relation：Jc =H-α, with the increase of applied field strengths, the critical current density (J of ybco filmc) rapid reduction.Therefore, realize The large-scale application of YBCO coating conductor, improves thin film performance under externally-applied magnetic field, becomes the key of research.
Wherein, carry out nano-particle doping, artificial introduces defect as pinning center inside thin film, can effectively change Performance under magnetic field for the kind ybco film.Therefore, research worker wishes to be introduced in effectively pin as much as possible inside thin film The heart is suppressing JcReduction off field outside.However, for the laminated film of single doping, doping is crossed conference and is led to cluster of grains The phenomenon such as poly-, stress is excessive, and then destroy YBCO texture.Single nano-particle doping reaches 7% about, JcValue just reaches peak Value, continues to increase doping, JcDecline it is impossible to improve YBCO current capacity off field outside further.The present invention provides a kind of The doping method of new double nano granule, on the premise of not destroying YBCO texture, effectively raises the pinning energy of thin film Power, improves the field performance of ybco film.
Content of the invention
It is an object of the invention under the current externally-applied magnetic field of solution, thin film pinning is limited, cannot continue raising current capacity Problem, a kind of strontium titanates (SrTiO of new type is provided3, STO) and lanthanum aluminate (LaAlO3, LAO) and the doping of double nano granule The preparation method of YBCO laminated film.
SrTiO provided by the present invention3With LaAlO3Doping is mutually perovskite structure, SrTiO3With YBCO lattice mismatch Spend for 1%, LaAlO3It is -0.86%, SrTiO with YBCO lattice mismatch3And LaAlO3Forming pressure respectively in YBCO lattice should Power and tension, while introducing a large amount of pinning defect, offset to the stress that YBCO is formed, therefore ybco film will not be because of Huge stress and destroy structure, more substantial artificial pinining center can be introduced.SrTiO simultaneously3And LaAlO3Lose with YBCO lattice Degree of joining all very littles, two kinds doping is mutually all easy and YBCO forms coherent boundary, and the atom on boundary arranges expansion or shrinkage to be passed through Good combination could be maintained, create elastic strain energy so that during less doping, larger dependent variable, shape just can be obtained The pinning effect of Cheng Geng great.Therefore, traditional single nano-particle doping, SrTiO are compared3With LaAlO3Double nano granule adulterates More substantial strain can be introduced as pinning center while maintaining YBCO texture, thus more effectively improving YBCO outfield Under current capacity.
The SrTiO that the present invention provides3With LaAlO3The preparation method of double nano granule doped YBCO laminated film, including step Suddenly as follows：
(1) prepare SrTiO3With LaAlO3Double nano granule doped YBCO compound precursor liquid：
1) prepare YBCO precursor liquid：By Y:Ba:Cu=1:2:3 stoichiometric proportion weighs four acetate hydrate yttriums, four hydrations Barium acetate and four hydrated copper acetates；Four acetate hydrate yttriums, four acetate hydrate barium are dissolved in deionized water, then according to four water Closing yttrium acetate and trifluoroacetic acid mol ratio is 1:The solution of gained is placed in after 60 DEG C of stirring in water bath 3h by 8 addition trifluoroacetic acids Distill on Rotary Evaporators, vapo(u)rizing temperature is 60 DEG C, then the white powder obtaining addition absolute methanol is dissolved again, obtain The precursor liquid A of Y and Ba salt；Four hydrated copper acetates and α-methacrylic acid are 1 in molar ratio:4 are added in absolute methanol, After abundant back flow reaction at 90 DEG C, carry out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, with no water beetle after being evaporated Alcohol dissolves, and obtains the precursor liquid B of Cu salt；Mixing precursor liquid A and B, distills at 40 DEG C, adds absolute methanol again molten after being evaporated Solution, repeatedly distills 3 times, obtains blue gel G；Finally use absolute methanol constant volume, obtain YBCO precursor liquid.
2) prepare SrTiO3The YBCO compound precursor liquid of doping：By step 1) described preparation blue gel G；By strontium acetate, Butyl titanate and acetylacetone,2,4-pentanedione are 1 according to mol ratio:1:1 is dissolved in a certain amount of propanoic acid, obtains SrTiO3Precursor liquid；Will SrTiO3Precursor liquid instills in blue gel G, uses absolute methanol constant volume, obtains the SrTiO that mol ratio is 20% that adulterates3Precursor liquid.
3) prepare LaAlO3The YBCO compound precursor liquid of doping：According to Y:Ba:Cu:La:Al=1:2:3:0.2:0.2 change Learn metering ratio and weigh four acetate hydrate yttriums, four acetate hydrate barium, lanthanum acetylacetone and aluminium acetylacetonate, be dissolved in deionized water In, then according to four acetate hydrate yttriums and trifluoroacetic acid mol ratio are 1:8 addition trifluoroacetic acids, after stirring 3h under 60 DEG C of water-baths Resulting solution is placed in distillation on Rotary Evaporators, vapo(u)rizing temperature is 60 DEG C, then the white powder obtaining is added no water beetle Alcohol dissolves again, obtains the precursor liquid A1 of Y and Ba salt；Four hydrated copper acetates and α-methacrylic acid are 1 in molar ratio:4 add Enter in absolute methanol, after abundant back flow reaction at 90 DEG C, carry out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, obtain the precursor liquid B1 of Cu salt；Mixing precursor liquid A1 and precursor liquid B1 is low at 40 DEG C Pressure distillation, adds absolute methanol again to dissolve, repeatedly distills 3 times, obtain blue gel after being evaporated, finally fixed with absolute methanol Hold, obtain the LAO precursor liquid that mol ratio is 20% that adulterates.
4) blend step 1) step 2) step 3) three kinds of precursor liquids preparing, obtaining STO molar content is 1%～10% He LAO molar content is the codope composite Y BCO precursor liquid of 1%～5% different proportion doping.
(2) precursor liquid coating：Precursor liquid prepared by step (1) is spun in substrate, obtains being attached to substrate surface Precursor film；Described substrate is LAO monocrystal chip or CeO2/YSZ/Y2O3/ Ni5W substrate；Spin coating revolution is 4000～6000rpm, Spin-coating time is 1～2min.
(3) heat treatment：Step (2) gained precursor film is placed in the quartz tube furnace being passed through dry oxygen, at room temperature It is raised to 150 DEG C with the speed of 10 DEG C/min.It is raised to 400 DEG C with the speed of 1.5～3 DEG C/min again, and is incubated 10min, work as temperature During higher than 150 DEG C, the oxygen being dried is changed into the oxygen of humidity, moisture content is 3.1%.Then again with the speed liter of 5 DEG C/min To 770～840 DEG C, it is incubated 2～3h.Wherein, in 400 DEG C to 500 DEG C temperature-rise periods, atmosphere is dry Ar/O2Atmosphere；Rise It is changed to the Ar/O of humidity to atmosphere when 550 DEG C2, moisture content is 7.4%, O2Partial pressure is 150PPM～500PPM；Be incubated is last Dampness is gained dry Ar/O by 30min2Atmosphere.After insulation finishes, sample cools to 500 DEG C with the furnace, and atmosphere is changed into drying O2, and it is incubated 3h at 500 DEG C, make YBCO complete oxygen uptake phase transformation, be changed into superconducting phase；Obtain the compound of double nano granule doping Ybco film.
Compared with prior art, the present invention has advantages below：
(1) present invention is a kind of new YBCO laminated film, and the doping of its nano-particle mutually can be played effective pinning and make With improving outer conductive capability off field.
(2) two kinds of adulterate mutually introducing compressive stress and tensions in YBCO lattice respectively that the present invention provides, corresponding two Plant local distortion of lattice and all can produce good pinning effect, so that the total pinning ability of thin film is strengthened；And in overall structure, two Plant stress to cancel out each other, prevent the internal stress of thin film excessive and cause cracking so that pinning level improves further.
(3) two kinds of doping of the present invention and the absolute value of YBCO lattice mismatch are both less than equal to 1%, doping Easily form coherent boundary with YBCO phase, the atom row on boundary will could maintain good combination by expansion or shrinkage, The elastic strain energy producing larger so that during less doping, larger dependent variable just can be obtained, form bigger pinning effect Should.
(4) present invention adopts metal organic salt chemical solution method with low cost, introduces alloy in precursor aqueous solution, after Coated and heat treatment, obtains the ybco film with the doping of double nano granule.Compare very widely used today physical deposition skill Art, has the advantages that equipment is simple, with low cost, thin film composition is easy to control and can arbitrarily change alloy proportioning it is easy to reality Now prepare on a large scale.
With reference to the accompanying drawings and detailed description the present invention is said further in detail.
Brief description
The SrTiO that Fig. 1, embodiment 1 obtain3With LaAlO3Double nano granule doped YBCO laminated film and single doping SrTiO3、LaAlO3And the J of pure ybco filmcCurve comparison figure (77K).
The SrTiO that Fig. 2, embodiment 2 obtain3With LaAlO3The SEM figure of double nano granule doped YBCO laminated film.
The SrTiO that Fig. 3, embodiment 3 obtain3With LaAlO3The pining force of double nano granule doped YBCO laminated film is with outer Plus changes of magnetic field figure.
Specific embodiment
With reference to embodiment, the present invention is described further, but the present invention is not limited to following examples.
Embodiment 1
(1) prepare SrTiO3And LaAlO3Double nano granule doped YBCO compound precursor liquid：
1) prepare YBCO precursor liquid：0.845g tetra- acetate hydrate yttrium, 1.275g tetra- acetate hydrate barium are dissolved in deionization In water, add 3.5ml trifluoroacetic acid, after 60 DEG C of stirring in water bath 3h, the solution of gained is placed in distillation on Rotary Evaporators, steams Evaporate temperature and be 60 DEG C, the white powder obtaining addition absolute methanol is dissolved again, obtains the precursor liquid A of Y and Ba salt；Will 1.497g tetra- hydrated copper acetate and 2.582g α-methacrylic acid are added in absolute methanol, abundant back flow reaction 3h at 90 DEG C Carry out 3 distillations afterwards on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, before obtaining Cu salt Drive liquid B；Mixing precursor liquid A and B, low-pressure distillation at 40 DEG C, add absolute methanol again to dissolve after being evaporated, repeatedly distill 3 times, Obtain blue gel G；Finally use absolute methanol constant volume, obtain YBCO precursor liquid.
2) prepare SrTiO3The YBCO compound precursor liquid of doping：By step 1) described preparation blue gel G；Weigh 1.029g Strontium acetate, 1.702g butyl titanate and 0.501g acetylacetone,2,4-pentanedione are dissolved in 10ml propanoic acid, obtain SrTiO3Precursor liquid；Take 1mlSrTiO3Precursor liquid, instills in blue gel G, is settled to 10ml with absolute methanol, and obtaining doping mol ratio is 20% SrTiO3The YBCO compound precursor liquid of doping.
3) prepare LaAlO3The YBCO compound precursor liquid of doping：0.845g tetra- acetate hydrate yttrium, 1.275g tetra- are hydrated second Sour barium, 0.218g lanthanum acetylacetone and 0.162g aluminium acetylacetonate are dissolved in deionized water, add 4ml trifluoroacetic acid, through 60 After DEG C stirring in water bath 3h, the solution of gained is placed in distillation on Rotary Evaporators, vapo(u)rizing temperature is 60 DEG C, by the white powder obtaining End adds absolute methanol again to dissolve, and obtains precursor liquid A1；By 1.497g tetra- hydrated copper acetate and 2.582g α-methacrylic acid It is added in absolute methanol, after abundant back flow reaction 3h at 90 DEG C, carries out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, obtain the precursor liquid B1 of Cu salt；Mixing precursor liquid A1 and B1, at 40 DEG C, low pressure is steamed Evaporate, add absolute methanol again to dissolve after being evaporated, repeatedly distill 3 times, finally use absolute methanol constant volume, obtaining doping mol ratio is 20% LAO precursor liquid.
4) 14 are pressed:1:5 volume ratio blend step 1), step 2) and step 3) obtained by three kinds of precursor liquids, can get The codope composite Y BCO precursor liquid that STO molar content is 1% and LAO molar content is 5%.
(2) precursor liquid coating：Precursor liquid prepared by step (1) is spun on LAO monocrystal chip, obtains being attached to substrate table The precursor film in face；Spin coating revolution is 4000rpm, and spin-coating time is 2min.
(3) heat treatment：Step (2) gained precursor film is placed in the quartz tube furnace being passed through dry oxygen, at room temperature It is raised to 150 DEG C with the speed of 10 DEG C/min.It is raised to 400 DEG C with the speed of 2 DEG C/min again, and is incubated 10min, when temperature is higher than When 150 DEG C, the oxygen being dried is changed into the oxygen of humidity, moisture content is 3.1%.Then risen to the speed of 5 DEG C/min again 820 DEG C, it is incubated 3h.Wherein, in 400 DEG C to 500 DEG C temperature-rise periods, atmosphere is dry Ar/O2Atmosphere；When rising to 550 DEG C Atmosphere is changed to the Ar/O of humidity2, moisture content is 7.4%, O2Partial pressure is 200PPM；Dampness is gained dry by the last 30min of insulation Dry Ar/O2Atmosphere.After insulation finishes, sample cools to 500 DEG C with the furnace, and atmosphere is changed into dry O2, and be incubated at 500 DEG C 3h, makes YBCO complete oxygen uptake phase transformation, is changed into superconducting phase；Obtain the composite Y BCO thin film of double nano granule doping.
The ybco film of 1%STO+5%LAO doping is thin with single doping 1%STO, single doping 5%LAO and pure YBCO The J of filmcCurve comparison figure is as shown in Figure 1.As illustrated, under the conditions of 77K, self-fields, pure ybco film and single doped samples JcValue Difference is inconspicuous, all reaches 3.0 × 106A/cm2, and 1%STO+5%LAO double nano granule doped samples JcBe worth for 5.5 × 106A/cm2, higher than single doped samples and pure YBCO sample.Under condition of external field, the superconductivity of codope sample is far above appoints One single doping and pure YBCO sample, under the conditions of 77K, 1T, double nano granule doped samples JcIt is worth 3.4 times for pure ybco film, Reach 1.7 × 106A/cm2.
Embodiment 2
(1) prepare SrTiO3And LaAlO3Double nano granule doped YBCO compound precursor liquid：
1) prepare YBCO precursor liquid：0.845g tetra- acetate hydrate yttrium, 1.275g tetra- acetate hydrate barium are dissolved in deionization In water, add 3.5ml trifluoroacetic acid, after 60 DEG C of stirring in water bath 3h, the solution of gained is placed in distillation on Rotary Evaporators, steams Evaporate temperature and be 60 DEG C, the white powder obtaining addition absolute methanol is dissolved again, obtains the precursor liquid A of Y and Ba salt；Will 1.497g tetra- hydrated copper acetate and 2.582g α-methacrylic acid are added in absolute methanol, abundant back flow reaction 3h at 90 DEG C Carry out 3 distillations afterwards on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, before obtaining Cu salt Drive liquid B；Mixing precursor liquid A and B, low-pressure distillation at 40 DEG C, add absolute methanol again to dissolve after being evaporated, repeatedly distill 3 times, Obtain blue gel G；Finally use absolute methanol constant volume, obtain YBCO precursor liquid.
2) prepare SrTiO3The YBCO compound precursor liquid of doping：By step 1) described preparation blue gel G；Weigh 1.029g Strontium acetate, 1.702g butyl titanate and 0.501g acetylacetone,2,4-pentanedione are dissolved in 10ml propanoic acid, obtain SrTiO3Precursor liquid；Take 1mlSrTiO3Precursor liquid, instills in blue gel G, is settled to 10ml with absolute methanol, and obtaining doping mol ratio is 20% SrTiO3The YBCO compound precursor liquid of doping.
3) prepare LaAlO3The YBCO compound precursor liquid of doping：0.845g tetra- acetate hydrate yttrium, 1.275g tetra- are hydrated second Sour barium, 0.218g lanthanum acetylacetone and 0.162g aluminium acetylacetonate are dissolved in deionized water, add 4ml trifluoroacetic acid, through 60 After DEG C stirring in water bath 3h, the solution of gained is placed in distillation on Rotary Evaporators, vapo(u)rizing temperature is 60 DEG C, by the white powder obtaining End adds absolute methanol again to dissolve, and obtains precursor liquid A1；By 1.497g tetra- hydrated copper acetate and 2.582g α-methacrylic acid It is added in absolute methanol, after abundant back flow reaction 3h at 90 DEG C, carries out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, obtain the precursor liquid B1 of Cu salt；Mixing precursor liquid A1 and B1, at 40 DEG C, low pressure is steamed Evaporate, add absolute methanol again to dissolve after being evaporated, repeatedly distill 3 times, finally use absolute methanol constant volume, obtaining doping mol ratio is 20% LAO precursor liquid.
4) 9 are pressed:10:1 volume ratio blend step 1), step 2) and step 3) obtained by three kinds of precursor liquids, can get The codope composite Y BCO precursor liquid that STO molar content is 10% and LAO molar content is 1%.
(2) precursor liquid coating：Precursor liquid prepared by step (1) is spun on CeO2/YSZ/Y2O3On/Ni5W substrate, obtain It is attached to the precursor film of substrate surface；Spin coating revolution is 6000rpm, and spin-coating time is 1min.
(3) heat treatment：Step (2) gained precursor film is placed in the quartz tube furnace being passed through dry oxygen, at room temperature It is raised to 150 DEG C with the speed of 10 DEG C/min.It is raised to 400 DEG C with the speed of 1.5 DEG C/min again, and is incubated 10min, when temperature is higher than When 150 DEG C, the oxygen being dried is changed into the oxygen of humidity, moisture content is 3.1%.Then risen to the speed of 5 DEG C/min again 770 DEG C, it is incubated 3h.Wherein, in 400 DEG C to 500 DEG C temperature-rise periods, atmosphere is dry Ar/O2Atmosphere；When rising to 550 DEG C Atmosphere is changed to the Ar/O of humidity2, moisture content is 7.4%, O2Partial pressure 150PPM；Dampness is gained drying by the last 30min of insulation Ar/O2Atmosphere.After insulation finishes, sample cools to 500 DEG C with the furnace, and atmosphere is changed into dry O2, and it is incubated 3h at 500 DEG C, Make YBCO complete oxygen uptake phase transformation, be changed into superconducting phase；Obtain the composite Y BCO thin film of double nano granule doping.
Fig. 2 is in CeO2/YSZ/Y2O3The SEM of the ybco film of doping 10%STO+1%LAO of preparation on/Ni5W substrate Figure.It can be seen that film surface is smooth, crackle, no a-b axialite do not occur, have a small amount of hole to occur.
Embodiment 3
(1) prepare SrTiO3And LaAlO3Double nano granule doped YBCO compound precursor liquid：
1) prepare YBCO precursor liquid：0.845g tetra- acetate hydrate yttrium, 1.275g tetra- acetate hydrate barium are dissolved in deionization In water, add 3.5ml trifluoroacetic acid, after 60 DEG C of stirring in water bath 3h, the solution of gained is placed in distillation on Rotary Evaporators, steams Evaporate temperature and be 60 DEG C, the white powder obtaining addition absolute methanol is dissolved again, obtains the precursor liquid A of Y and Ba salt；Will 1.497g tetra- hydrated copper acetate and 2.582g α-methacrylic acid are added in absolute methanol, abundant back flow reaction 3h at 90 DEG C Carry out 3 distillations afterwards on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, before obtaining Cu salt Drive liquid B；Mixing precursor liquid A and B, low-pressure distillation at 40 DEG C, add absolute methanol again to dissolve after being evaporated, repeatedly distill 3 times, Obtain blue gel G；Finally use absolute methanol constant volume, obtain YBCO precursor liquid.
2) prepare SrTiO3The YBCO compound precursor liquid of doping：By step 1) described preparation blue gel G；Weigh 1.029g Strontium acetate, 1.702g butyl titanate and 0.501g acetylacetone,2,4-pentanedione are dissolved in 10ml propanoic acid, obtain SrTiO3Precursor liquid；Take 1mlSrTiO3Precursor liquid, instills in blue gel G, is settled to 10ml with absolute methanol, and obtaining doping mol ratio is 20% SrTiO3The YBCO compound precursor liquid of doping.
3) prepare LaAlO3The YBCO compound precursor liquid of doping：0.845g tetra- acetate hydrate yttrium, 1.275g tetra- are hydrated second Sour barium, 0.218g lanthanum acetylacetone and 0.162g aluminium acetylacetonate are dissolved in deionized water, add 4ml trifluoroacetic acid, through 60 After DEG C stirring in water bath 3h, the solution of gained is placed in distillation on Rotary Evaporators, vapo(u)rizing temperature is 60 DEG C, by the white powder obtaining End adds absolute methanol again to dissolve, and obtains precursor liquid A1；By 1.497g tetra- hydrated copper acetate and 2.582g α-methacrylic acid It is added in absolute methanol, after abundant back flow reaction 3h at 90 DEG C, carries out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, dissolved with absolute methanol after being evaporated, obtain the precursor liquid B1 of Cu salt；Mixing precursor liquid A1 and precursor liquid B1, at 40 DEG C Low-pressure distillation, adds absolute methanol again to dissolve, repeatedly distills 3 times, finally use absolute methanol constant volume, obtain doping and rub after being evaporated You are than the LAO precursor liquid for 20%.
4) 5 are pressed:4:1 volume ratio blend step 1), step 2) and step 3) obtained by three kinds of precursor liquids, can get The codope composite Y BCO precursor liquid that STO molar content is 8% and LAO molar content is 2%；
(2) precursor liquid coating：Precursor liquid prepared by step (1) is spun on LAO monocrystal chip, obtains being attached to substrate table The precursor film in face；Spin coating revolution is 6000rpm, and spin-coating time is 2min；
(3) heat treatment：Step (2) gained precursor film is placed in the quartz tube furnace being passed through dry oxygen, at room temperature It is raised to 150 DEG C with the speed of 10 DEG C/min.It is raised to 400 DEG C with the speed of 3 DEG C/min again, and is incubated 10min, when temperature is higher than When 150 DEG C, the oxygen being dried is changed into the oxygen of humidity, moisture content is 3.1%.Then risen to the speed of 5 DEG C/min again 840 DEG C, it is incubated 3h.Wherein, in 400 DEG C to 500 DEG C temperature-rise periods, atmosphere is dry Ar/O2Atmosphere；When rising to 550 DEG C Atmosphere is changed to the Ar/O of humidity2, moisture content is 7.4%, O2Partial pressure is 400PPM；Dampness is gained dry by the last 30min of insulation Dry Ar/O2Atmosphere.After insulation finishes, sample cools to 500 DEG C with the furnace, and atmosphere is changed into dry O2, and be incubated at 500 DEG C 3h, makes YBCO complete oxygen uptake phase transformation, is changed into superconducting phase；Obtain the composite Y BCO thin film of double nano granule doping.
Fig. 3 is the pining force of the ybco film of 8%STO+2%LAO double nano granule doping with changes of magnetic field curve.77K Under, the maximum pining force of the ybco film of 8%STO+2%LAO double nano granule doping is 6.15GN/m3, it is pure ybco film 3.42 times.Additionally, maximum pining force moves to high field direction, laminated film is moved to by the 0.79T of pure ybco film 1.97T.

Claims (1)

1. a kind of SrTiO3With LaAlO3The preparation method of double nano granule doped YBCO laminated film is it is characterised in that include step Suddenly as follows：
(1) prepare SrTiO3With LaAlO3Double nano granule doped YBCO compound precursor liquid：
1) prepare YBCO precursor liquid：By Y:Ba:Cu=1:2:3 stoichiometric proportion weighs four acetate hydrate yttriums, four acetate hydrate Barium and four hydrated copper acetates；Four acetate hydrate yttriums, four acetate hydrate barium are dissolved in deionized water, then according to four hydration second Sour yttrium and trifluoroacetic acid mol ratio are 1:The solution of gained is placed in rotation after 60 DEG C of stirring in water bath 3h by 8 addition trifluoroacetic acids On evaporimeter distill, vapo(u)rizing temperature be 60 DEG C, then by the white powder obtaining addition absolute methanol again dissolve, obtain Y and The precursor liquid A of Ba salt；Four hydrated copper acetates and α-methacrylic acid are 1 in molar ratio:4 are added in absolute methanol, 90 After abundant back flow reaction at DEG C, carry out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, uses absolute methanol after being evaporated Dissolving, obtains the precursor liquid B of Cu salt；Mixing precursor liquid A and B, distills at 40 DEG C, adds absolute methanol again molten after being evaporated Solution, repeatedly distills 3 times, obtains blue gel G；Finally use absolute methanol constant volume, obtain YBCO precursor liquid；
2) prepare SrTiO3The YBCO compound precursor liquid of doping：By step 1) described preparation blue gel G；By strontium acetate, metatitanic acid four Butyl ester and acetylacetone,2,4-pentanedione are 1 according to mol ratio:1:1 is dissolved in propanoic acid, obtains SrTiO3Precursor liquid；By SrTiO3Forerunner's drop Enter in blue gel G, use absolute methanol constant volume, obtain the SrTiO that mol ratio is 20% that adulterates3Precursor liquid；
3) prepare LaAlO3The YBCO compound precursor liquid of doping：According to Y:Ba:Cu:La:Al=1:2:3:0.2:0.2 chemistry meter Amount ratio weighs four acetate hydrate yttriums, four acetate hydrate barium, lanthanum acetylacetone and aluminium acetylacetonate, is dissolved in deionized water, so It is 1 according to four acetate hydrate yttriums and trifluoroacetic acid mol ratio afterwards:8 addition trifluoroacetic acids, by institute after stirring 3h under 60 DEG C of water-baths Obtain solution and be placed in distillation on Rotary Evaporators, vapo(u)rizing temperature is 60 DEG C, then the white powder obtaining is added absolute methanol weight New dissolving, obtains the precursor liquid A1 of Y and Ba salt；Four hydrated copper acetates and α-methacrylic acid are 1 in molar ratio:4 are added to In absolute methanol, after abundant back flow reaction at 90 DEG C, carry out 3 distillations on a rotary evaporator, vapo(u)rizing temperature is 40 DEG C, steams With absolute methanol dissolving after dry, obtain the precursor liquid B1 of Cu salt；Mixing precursor liquid A1 and precursor liquid B1, at 40 DEG C, low pressure is steamed Evaporate, add absolute methanol again to dissolve after being evaporated, repeatedly distill 3 times, obtain blue gel, finally use absolute methanol constant volume, obtain The LAO precursor liquid being 20% to doping mol ratio；
4) blend step 1), step 2) and step 3) three kinds of precursor liquids preparing, obtaining STO molar content is 1%～10% He LAO molar content is the codope composite Y BCO precursor liquid of 1%～5% different proportion doping；
(2) precursor liquid coating：Precursor liquid prepared by step (1) is spun in substrate, obtains the forerunner being attached to substrate surface Film；Described substrate is LAO monocrystal chip or CeO2/YSZ/Y2O3/ Ni5W substrate；Spin coating revolution is 4000～6000rpm, spin coating Time is 1～2min；
(3) heat treatment：Step (2) gained precursor film is placed in the quartz tube furnace being passed through dry oxygen, at room temperature with 10 DEG C/speed of min is raised to 150 DEG C；It is raised to 400 DEG C with the speed of 1.5～3 DEG C/min again, and is incubated 10min, when temperature is higher than When 150 DEG C, the oxygen being dried is changed into the oxygen of humidity, moisture content is 3.1%；Then risen to the speed of 5 DEG C/min again 770～840 DEG C, it is incubated 2～3h；Wherein, in 400 DEG C to 500 DEG C temperature-rise periods, atmosphere is dry Ar/O2Atmosphere；Rise to When 550 DEG C, atmosphere is changed to the Ar/O of humidity2, moisture content is 7.4%, O2Partial pressure is 150PPM～500PPM；Be incubated is last Dampness is gained dry Ar/O by 30min2Atmosphere；After insulation finishes, sample cools to 500 DEG C with the furnace, and atmosphere is changed into drying O2, and it is incubated 3h at 500 DEG C, make YBCO complete oxygen uptake phase transformation, be changed into superconducting phase；Obtain the compound of double nano granule doping Ybco film.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451450B1 (en) * 1995-04-10 2002-09-17 Ut-Battelle, Llc Method of depositing a protective layer over a biaxially textured alloy substrate and composition therefrom
CN102142300A (en) * 2010-12-12 2011-08-03 西北有色金属研究院 Second-phase nanoparticle doped YBCO (yttrium barium copper oxide) film and preparation method thereof
CN105198401A (en) * 2015-10-14 2015-12-30 北京工业大学 Method for preparing double mismatch multi-element doped composite YBCO thin film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451450B1 (en) * 1995-04-10 2002-09-17 Ut-Battelle, Llc Method of depositing a protective layer over a biaxially textured alloy substrate and composition therefrom
CN102142300A (en) * 2010-12-12 2011-08-03 西北有色金属研究院 Second-phase nanoparticle doped YBCO (yttrium barium copper oxide) film and preparation method thereof
CN105198401A (en) * 2015-10-14 2015-12-30 北京工业大学 Method for preparing double mismatch multi-element doped composite YBCO thin film

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