CN100373649C - Method for preparing high temperature superconductor thick film of Ba/YCu with large area by using electrophoresis technique - Google Patents

Method for preparing high temperature superconductor thick film of Ba/YCu with large area by using electrophoresis technique Download PDF

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CN100373649C
CN100373649C CNB021163243A CN02116324A CN100373649C CN 100373649 C CN100373649 C CN 100373649C CN B021163243 A CNB021163243 A CN B021163243A CN 02116324 A CN02116324 A CN 02116324A CN 100373649 C CN100373649 C CN 100373649C
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yba
film
thick film
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high temperature
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CN1447451A (en
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朱亚彬
熊季午
周岳亮
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Institute of Physics of CAS
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Abstract

The present invention relates to a method for preparing large-scale high-temperature superconducting Ba-Y-Cu oxygen thick films by electrophoretic techniques. The method comprises: grinding YBa2Cu3O<7-delta> powder previously sintered until particle sizes are less than 0.1-10 mu m; vaporizing a layer of metal film on a MgO single-crystal substrate which is fixed to a cathode for sstandby; mixing the YBa2Cu3O<7-delta> powder with organic solvents according to a mixture ratio of 20 g/g/L; stirring mixtures to make the YBa2Cu3O<7-delta> powder completely dispersed uniformly in the organic solvents to prepare YBa2Cu3O<7-delta> electrophoretic liquid; putting prepared YBa2Cu3O<7-delta> electrophoretic liquid and an electrode provided with the substrate into an electrophoretic tank washed cleanly; electrifying 900 V of direct current on the anode and the cathode of the electrode and keeping sedimentation time for 5 to 1600 seconds to deposit a layer of uniform YBa2Cu3O<7-delta> film on the substrate. The film prepared by adopting the method has the advantages of superior superconducting performance and uniform and compact texture; the invention has the advantages of simple technology, rapid growth of film layers, controllable film thickness and low cost, and is suitable for industrialized application.

Description

Adopt electrophoretic techniques to prepare the method for large area high temperature superconductive barium-yttrium-copper oxide thick film
Technical field
The present invention relates to the preparation field of high temperature superconducting film, particularly relate to electrophoretic techniques and prepare large area high temperature superconductive barium-yttrium-copper oxide (YBa 2Cu 3O 7-δ) method of thick film.
Background technology
YBa 2Cu 3O 7-δSuperconducting film because its higher superconducting transition temperature, high critical current density are widely used in the microwave and the communications field, has irreplaceable status especially in microwave devices such as filter.Prepare YBa now 2Cu 3O 7-δFilm often adopts pulsed laser deposition (hereinafter to be referred as PLD) and magnetron sputtering method etc.The PLD method can grow the good YBa of superconductivity 2Cu 3O 7-δFilm, but its speed of growth can slow down slowly with the increase of rete area.And the preparation difficulty becomes big with the rete area and thickening increases sharply.In addition, the PLD method also needs expensive high-power excimer laser, as document 1:Preparation of Y-Ba-Cu oxide superconductor thin filmsusing pulsed laser evaporation from high Tc bulk material, Appl.Phys.Lett., 51, introduced in 619,1987.The another kind of magnetron sputtering method that adopts prepares YBa 2Cu 3O 7-δFilm is as document 2:Growth and characterization of a-axisoriented YBa 2Cu 3O 7-δThin films on (100) LaSrGaO 4Substrates, PhysicaC is introduced in 280,167,1997, the YBa of this method preparation 2Cu 3O 7-δThe film surface of film is very smooth, but forms reverse sputtering easily in preparation process, makes YBa 2Cu 3O 7-δThe quality of film descends.In addition, the evaporation rate of each element is different, and the composition of film is departed from.Therefore, through facts have proved that above method is not growth YBa 2Cu 3O 7-δThe Perfected process of superconducting thick-film.
Summary of the invention
Can grow the good YBa of superconductivity though the objective of the invention is to overcome the PLD method 2Cu 3O 7-δFilm, but its speed of growth can increase become slow with the rete area, and also the preparation difficulty is with shortcoming that the rete area becomes greatly and thickening increases sharply and the shortcoming that also needs expensive high-power excimer laser; In addition, also be to overcome the film of magnetron sputtering method in preparation process and form reverse sputtering easily, the quality of film is descended and the evaporation rate of each element different, the shortcoming that the composition of film is departed from; Reach for the area for preparing superconducting film in the size range of 5mm-200mm, realize YBa simultaneously again 2Cu 3O 7-δThe superconduction thickness is to 800nm-20 μ m, thereby provides a kind of employing electrophoretic techniques to prepare large tracts of land YBa 2Cu 3O 7-δThe method of thick film.
The present invention is achieved in that employing electrophoretic techniques provided by the invention prepares large tracts of land YBa 2Cu 3O 7-δThe method of thick film may further comprise the steps:
The first step is with the YBa that sinters in advance 2Cu 3O 7-δPowder fully grinds, and reaching granularity less than 0.1-10 μ m, otherwise can cause film inhomogeneous;
Second step, deposit layer of metal film with common evaporation earlier on the MgO single crystal substrates, this metal film comprises: Ag, or other does not destroy the metal of barium-yttrium-copper oxide superconductivity, for example: Pt, Au, Cu, Ir, Al, the film of materials such as Pd is fixed on this substrate that has plated film on the negative pole, is placed in the clean vessel standby;
In the 3rd step, get the prepared YBa of step 1 2Cu 3O 7-δPowder is pressed YBa 2Cu 3O 7-δPowder mixes with organic solvent, and its mixed proportion is the 2-40 grams per liter, and described organic solvent comprises: acetone, alcohol, chloroform or dichloroethylene, high-purity water or the like, all organic solvents can, stir then and make YBa 2Cu 3O 7-δIn organic solvent, be uniformly dispersed fully, be mixed with YBa 2Cu 3O 7-δElectrophoresis liquid;
The 4th step, the YBa that step 3 is prepared 2Cu 3O 7-δElectrophoresis liquid 4 is put into clean tiselius apparatus, stirs once more and makes it more even; The electrode that substrate is housed for preparing is prevented in the tiselius apparatus that positive and negative electrode connects a high-voltage DC power supply; The direct current of logical 20-900V on electrode, and maintenance is then switched on sedimentation time 5-1600 second, deposition layer of even YBa on substrate 2Cu 3O 7-δFilm;
In the 5th step, step 4 has been deposited YBa 2Cu 3O 7-δFilm is placed in the sintering furnace, furnace temperature is raised to 1000-1106 ℃ at the programming rate with 300-400 degree centigrade/hour, and be incubated 30 minutes, reduce to 990 ℃ with 300 degrees centigrade/hour cooling rate then, reduce to 950 ℃ with 1 degree centigrade/hour speed again, with 300 degrees centigrade of/hour cooling rate cool to room temperature, obtain being deposited on on-chip YBa at last 2Cu 3O 7-δThick film.
In order to obtain high superconduction critical temperature T C0, high critical current densities J cWell-crystallized, fine and close YBa 2Cu 3O 7-δThick film also comprises the 6th step: with YBa 2Cu 3O 7-δThick film is placed in the sintering furnace, and furnace temperature and charges into oxygen under keeping 300 ℃ to 400 ℃, the flow velocity of its oxygen be the 0.1-25 liter/minute, carry out after annealing and handle.
Described tiselius apparatus, as shown in Figure 1; Limit the size of electrode according to the size of required preparation thick film, positive and negative electrode (2,3) is by making with a kind of sheet metal strip, and positive and negative electrode is spaced apart 3-5cm, with negative pole 3 lower ends with the side has bent so that substrate can be fixed on the negative pole, insert in the tiselius apparatus together;
Described organic solvent purity is 99.99%.
Described metal material as electrode requires chemical property highly stable, and has certain pliability, as copper, silver, stainless steel etc.
Advantage of the present invention:
Employing electrophoretic techniques of the present invention prepares the method for large area high temperature superconductive barium-yttrium-copper oxide thick film, since the high deposition rate of electrophoresis, feasible growth YBa 2Cu 3O 7-δThe thickness of film increases rapidly, and the thickness of film controls easily, and the size of film is unrestricted, so easy growth thick film; This method technology is simple, is particularly suitable for suitability for industrialized production; The thick film quality even compact of being grown, function admirable, cheap.
Description of drawings
Fig. 1 is the tiselius apparatus structural representation
Drawing is described as follows:
The anodal 3-negative pole of 1-high voltage source 2-4-electrophoresis liquid
Embodiment
Embodiment 1: prepare YBa on the MgO of 10mm * 10mm substrate 2Cu 3O 7-δSuperconducting thick-film.
What present embodiment used is the tiselius apparatus shown in Fig. 1, and the MgO substrate of 10mm * 10mm * 0.5mm is steamed last layer Ag in advance.The first step is with 2.45 gram YBa 2Cu 3O 7-δPowder, fully grinding makes its granularity less than 2 μ m, then with ground YBa 2Cu 3O 7-δPowder mixes with 125-1000 milliliter acetone (purity 99.99%), pours tiselius apparatus into after stirring with glass bar.Second step is with the positive and negative electrode of the argent of the long 5cm of the wide 1.5cm of thick 0.3mm cleaning as tiselius apparatus.The lower end of negative pole and side are bent with fixed substrate, and the MgO substrate that is coated with Ag is fixed on the negative pole.In the 3rd step, on electrode, add 900 volt direct currents and kept 10 minutes.On substrate, just deposited the thick YBa of the about 10 μ m of one deck 2Cu 3O 7-δFilm.The 4th step, the YBa that deposition is good 2Cu 3O 7-δFilm is placed in the sintering furnace, furnace temperature is raised to 1106 ℃ at the programming rate with 300-400 degree centigrade/hour, and keep half an hour, reduce to 990 ℃ with 300 degrees centigrade/hour cooling rate then, reduce to 950 ℃ with 1 degree centigrade/hour speed again, with 300 degrees centigrade of/hour cool to room temperature, be deposited on on-chip YBa so at last 2Cu 3O 7-δThe just preliminary preparation of thick film is finished.Also comprised for the 5th step, in oxygen, temperature keeps 400 ℃ to carry out the after annealing processing, and the flow velocity of oxygen is 0.5 liter/minute, the YBa that obtains 2Cu 3O 7-δThe thick film even compact, superconducting transition temperature 91K, critical current density is 1.5 * 10 6A/cm 2Illustrate that this method obtains the large tracts of land YBa of function admirable 2Cu 3O 7-δThick film,, good reproducibility simple through this method of experiment confirm repeatedly.
Embodiment 2: prepare YBa on the big substrate of the MgO of 150mm * 150mm 2Cu 3O 7-δSuperconducting thick-film.
Present embodiment uses is tiselius apparatus among Fig. 1.Method is similar to Example 1, steams one deck Pt at the MgO substrate in advance.Tiselius apparatus is identical with embodiment 1, YBa 2Cu 3O 7-δPowder particle size is less than 0.5 μ m, electrophoresis solvent chloroform.The MgO substrate that is coated with Pt is fixed on the negative pole, is connected with 900 volts of voltages between the both positive and negative polarity, kept 30 minutes.On substrate, just deposited the thick YBa of the about 800nm of one deck 2Cu 3O 7-δFilm.To deposit YBa 2Cu 3O 7-δBeing placed in the sintering furnace of film, furnace temperature is raised to 1080 ℃ at the programming rate with 300-400 degree centigrade/hour, and keep half an hour, reduce to 990 ℃ with 300 degrees centigrade/hour cooling rate then, reduce to 950 ℃ with 1 degree centigrade/hour speed again, at last with 300 degrees centigrade of/hour cool to room temperature, with this YBa 2Cu 3O 7-δThick film carries out after annealing in 350 ℃ of oxygen atmospheres handles, and the flow velocity of oxygen is 20 liters/minute, the YBa that obtains 2Cu 3O 7-δThick film even compact, superconducting transition temperature are distributed between 85K and the 92K.
Embodiment 3: the ybco film of growing on the nickel sheet of texture, MgO makes separator.
The tiselius apparatus of present embodiment among Fig. 1.Method is similar to Example 1, and at first the fine and close magnesia film uniformly of preparation (by Chinese patent application number: NO.01110033.8 makes) steams last layer Al with the MgO substrate.Tiselius apparatus is identical with embodiment 1, YBa 2Cu 3O 7-δPowder particle size is less than 8 μ m.Ag/MgO/Ni is fixed on the negative pole, is connected with 900 volts of voltages between the both positive and negative polarity, kept 10 minutes.On substrate, just deposited the thick YBa of the about 17 μ m of one deck 2Cu 3O 7-δTo deposit YBa 2Cu 3O 7-δBeing placed in the sintering furnace of film, furnace temperature is raised to 1050 ℃ at the programming rate with 300-400 degree centigrade/hour, and keep half an hour, reduce to 990 ℃ with 300 degrees centigrade/hour cooling rate then, reduce to 950 ℃ with 1 degree centigrade/hour speed again, at last with 300 degrees centigrade of/hour cool to room temperature, with this YBa 2Cu 3O 7-δThick film carries out after annealing in 350 ℃ of oxygen atmospheres handles, and the flow velocity of oxygen is 10 liters/minute, the YBa that obtains 2Cu 3O 7-δThe thick film even compact, superconducting transition temperature is distributed in 93K.Critical current density is 2.3 * 10 6A/cm 2

Claims (7)

1. adopt electrophoretic techniques to prepare the method for large area high temperature superconductive barium-yttrium-copper oxide thick film, it is characterized in that: may further comprise the steps:
The first step is with YBa 2Cu 3O 7-δPowder fully grinds, and reaches granularity less than 0.1-10 μ m;
Second step deposited layer of metal film with evaporation earlier on the MgO single crystal substrates, this substrate is fixed on the negative pole, was placed in the clean vessel standby;
In the 3rd step, get the prepared YBa of step 1 2Cu 3O 7-δPowder is pressed YBa 2Cu 3O 7-δPowder mixes for the 2-40 grams per liter with the organic solvent mixed proportion, mixes the back and stirs, and is mixed with YBa 2Cu 3O 7-δElectrophoresis liquid;
The 4th step, the YBa that step 3 is prepared 2Cu 3O 7-δElectrophoresis liquid (4) is put into clean tiselius apparatus with the electrode that substrate is housed, and stirs once more; The direct current of logical 20-900V deposits on the positive and negative electrode, and keeps energising sedimentation time 5-1600 second, deposition layer of even YBa on substrate 2Cu 3O 7-δFilm;
The 5th step, the YBa that step 4 deposition is good 2Cu 3O 7-δFilm is placed in the sintering furnace, furnace temperature is raised to 1000-1106 ℃ at the programming rate with 300-400 degree centigrade/hour, and be incubated 30 minutes, reduce to 990 ℃ with 300 degrees centigrade/hour cooling rate then, reduce to 950 ℃ with 1 degree centigrade/hour speed again, with 300 degrees centigrade of/hour cool to room temperature, obtain being deposited on on-chip YBa at last 2Cu 3O 7-δThick film.
2. prepare the method for large area high temperature superconductive barium-yttrium-copper oxide thick film by the described employing electrophoretic techniques of claim 1, it is characterized in that: also comprise the YBa that the 5th step is obtained 2Cu 3O 7-δThick film is placed on and carries out after annealing in the sintering furnace and handle, and furnace temperature remains under 300 to 400 ℃, and charges into oxygen, the flow velocity of its oxygen be the 0.1-25 liter/minute.
3. adopt electrophoretic techniques to prepare the method for large area high temperature superconductive barium-yttrium-copper oxide thick film by claim 1 or 2 described each, it is characterized in that: the metal film that deposits on the described MgO single crystal substrates comprises Ag, Pt, Au, Cu, Ir, Al or Pd.
4. adopt electrophoretic techniques to prepare the method for large area high temperature superconductive barium-yttrium-copper oxide thick film by claim 1 or 2 described each, it is characterized in that: described organic solvent comprises acetone, alcohol, chloroform or dichloroethylene.
5. the method for preparing large area high temperature superconductive barium-yttrium-copper oxide thick film by each described employing electrophoretic techniques in claim 1 or 2, it is characterized in that: the electrode in the described tiselius apparatus limits the size of electrode according to the size of required preparation thick film, positive and negative electrode is by making with a kind of sheet metal strip, and positive and negative electrode is spaced apart 3-5cm.
6. prepare the method for large area high temperature superconductive barium-yttrium-copper oxide thick film by each described employing electrophoretic techniques in claim 1 or 2, it is characterized in that: described organic solvent purity is 99.99%.
7. the method for preparing large area high temperature superconductive barium-yttrium-copper oxide thick film by each described employing electrophoretic techniques in claim 1 or 2, it is characterized in that: it is highly stable that described metal material as electrode has chemical property, and have certain flexible copper, silver, stainless steel material.
CNB021163243A 2002-03-26 2002-03-26 Method for preparing high temperature superconductor thick film of Ba/YCu with large area by using electrophoresis technique Expired - Fee Related CN100373649C (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0311804A1 (en) * 1987-09-17 1989-04-19 Siemens Aktiengesellschaft Method of making superconducting ceramic films
EP0382194A1 (en) * 1989-02-08 1990-08-16 Siemens Aktiengesellschaft Electrophoretic deposition of a superconducting coating under the influence of an external magnetic field

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0311804A1 (en) * 1987-09-17 1989-04-19 Siemens Aktiengesellschaft Method of making superconducting ceramic films
EP0382194A1 (en) * 1989-02-08 1990-08-16 Siemens Aktiengesellschaft Electrophoretic deposition of a superconducting coating under the influence of an external magnetic field

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
溶胶法合成YBCO微粉及电泳法制备厚膜. 陈凤翔，李能，陈名玲，林炳雄.中国稀土学报，第10卷第3期. 1992 *
用电泳法制备YBCO厚膜. 方家光，王蕾，刘梦林，郭增，黄贺生，杨燕池.低温与超导，第22卷第3期. 1994 *

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