JP2632409B2 - Method and apparatus for forming high temperature superconductor thick film - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for forming a high-temperature superconductor thick film and an apparatus for forming the same, and more particularly, to a gas provided with a co-evaporation source and a co-evaporation source. For example, by deposition method Bi _0.7 · Pb
_{The present} invention relates to a method and an apparatus for forming a thick film of a high-temperature superconducting material composed of a plurality of elements, such as a thick film of a _0.3 · Sr ₁ · Ca ₁ · Cu ₂ · O _Y- based superconductor.

(Prior Art) As a formation method of this kind, the present applicant has previously filed Japanese Patent Application No.
In 169119, each element constituting the superconducting material is separately heated and evaporated in an inert gas atmosphere to produce ultrafine particles, and the ultrafine particles of the element are separately transported while using the inert gas as a carrier gas. These are combined, the ultrafine particles are mixed at the composition ratio of the superconducting material, oxygen gas is further introduced into the carrier gas, and the mixture of the ultrafine particles is jetted from a nozzle onto a heated substrate to form the substrate. We have proposed a method for forming a superconductor thick film by depositing a film of ultrafine particles on it.

Further, as an apparatus for carrying out the formation method simultaneously with the proposal, as shown in FIG. 3, an ultrafine particle generation chamber a is provided for each element constituting the superconductor material, and the element is heated in each chamber a. An evaporation source b to be accommodated for evaporation, a vacuum evacuation device c for evacuating the chamber a, an inert gas introduction pipe d, and a transport pipe e for leading out the generated ultrafine particles together with the inert gas are provided. An ultrafine particle generating unit, an ultrafine particle mixing / conveying unit connected to an intermediate chamber i provided with an oxygen gas introducing pipe f and a conveying pipe h having a nozzle g at the tip, and a transport pipe h having a nozzle g at the tip. The nozzle g is guided into a film forming chamber l provided with a substrate holding device j and a vacuum exhaust device k which can be heated freely.
And an ultra-fine particle film forming portion having the tip of the substrate close to the surface of the substrate m held by the substrate holding device j. In the figure, n is an ultrafine particle generation chamber a
A heating device for heating the element o in the evaporation source b, p is a supply cylinder of an inert gas to the ultrafine particle generation chamber a, q is a supply cylinder of an oxygen gas to the intermediate chamber i, and r is a film forming chamber. A supply source cylinder of oxygen gas into m, s denotes a heating device for the substrate m, t denotes a main transport pipe, and u denotes a double pipe section.

(Problems to be Solved by the Invention) However, in the method of forming a superconductor thick film, the generation of the ultrafine particles of the elements constituting the superconducting material is separately heated for each element in an inert gas atmosphere. since so as to evaporate, for example, _{Bi 0.7 · Pb 0.3 · Sr 1} · Ca 1 · Cu 2 · O Y -based superconductor thick five except the elements constituting the superconducting material is an oxygen like film (Bi , Pb, Sr, Ca, Cu), there is a problem that the generation of each ultra-fine particle is complicated because the generation of ultra-fine particles must be performed separately and simultaneously in five places.

In addition, since the forming apparatus uses the evaporation source b for generating ultrafine particles of the element constituting the superconducting material as a separate evaporation source for each elemental material, for example, the superconducting material such as the thick film is used. When the elements constituting the material are five types as described above, the ultrafine particle generation chamber a provided with the evaporation source b for generating the ultrafine particles has a size of 5 mm.
And ancillary equipment such as a vacuum exhaust device c, an inert gas introduction pipe d, and a transport pipe e for the generated ultrafine particles are required for each of the generation chambers a. However, there are problems such as that the device is large and complicated, and that the installation area of the entire device becomes large.

An object of the present invention is to provide a method for forming a high-temperature superconductor thick film that has solved the above-mentioned problems and a forming apparatus suitable for performing the method.

(Means for Solving the Problems) The present invention proposes a formation method for achieving the above-mentioned object, in which a plurality of elements constituting a high-temperature superconducting material are vaporized by one evaporation in an ultrafine particle generation chamber in an inert gas atmosphere. The mixture is heated and evaporated so as to have a composition ratio of the high-temperature superconducting material at a source to form a mixture of ultrafine particles, and while the mixture of ultrafine particles is transported using the inert gas as a carrier gas, The method is characterized in that an oxygen gas is introduced, and a mixture of the ultrafine particles is sprayed from a nozzle onto a heated substrate together with a carrier gas containing an oxygen gas to form an ultrafine particle film on the substrate.

Another method is to heat and evaporate a plurality of elements constituting the high-temperature superconducting material at a plurality of evaporation sources in an ultrafine particle generation chamber in an inert gas atmosphere so as to have a composition ratio of the high-temperature superconducting material. To form a mixture of ultra-fine particles, while introducing the mixture of ultra-fine particles using the inert gas as a carrier gas, introducing oxygen gas into the carrier gas, and converting the mixture of ultra-fine particles into a carrier containing oxygen gas. The method is characterized in that an ultrafine particle film is adhered and formed on a substrate heated by spraying from a nozzle together with a gas onto the substrate.

In order to heat and evaporate (hereinafter referred to as co-evaporation) a plurality of elements with one evaporation source, the evaporation temperature of the elements, the composition ratio of the molten metal (raw material), the evaporation surface area and the pressure at the time of evaporation are adjusted to adjust the superconducting material. The composition ratio is set.

For example _{Bi 0.7 · Pb 0.3 · Sr 1} · Ca 1 · Cu 2 · O Y system 5 kinds of elements except oxygen as high temperature superconductor thick film (Bi, Pb, Sr, C
a, Cu) As shown in Table 1, two types of elements having substantially the same evaporation temperature and similar vapor pressures may be appropriately selected from the plurality of elements constituting the high-temperature superconducting material. In this case, Bi and Pb may be heated and evaporated (hereinafter referred to as simultaneous evaporation) from the same evaporation source, and Sr and Ca may be heated and evaporated from the same evaporation source.
The ratio of the amount of evaporation of both elements co-evaporated from the same evaporation source is determined by adjusting the mixing ratio of the elements in the raw material supplied to the evaporation source.

Further, when the means described above cannot be adopted because the vapor pressures of the elements constituting the high-temperature superconducting material are considerably different, the mixing ratio of the raw materials supplied to the same evaporation source is adjusted, and each of them is adjusted. The evaporation conditions for different elements are corrected to match the target evaporation rate.

For example, if _{Y 1 · Ba 2 · Cu 3} · O 7-X systems, such as high-temperature superconductor thick film, As shown in Table 2, the vapor pressures of Cu and Y are considerably different. However, in order to evaporate these two elements with the same evaporation source, the mixing ratio of both elements supplied to the evaporation source is adjusted. What is necessary is just to control the ratio of the amount of evaporation.

Further, the present invention proposes a forming apparatus for performing the forming method, wherein a plurality of elements constituting the high-temperature superconducting material are simultaneously heated and evaporated to a composition ratio of the high-temperature superconducting material to form a mixture of ultrafine particles. The ultrafine particle generation chamber equipped with one evaporation source to be generated has a vacuum exhaust device for evacuating the chamber, an inert gas introduction pipe, and a nozzle at the tip to inactivate the mixture of generated ultrafine particles. An ultra-fine particle generating unit connected to a transport pipe led out together with the gas, and a transport pipe having a nozzle at the tip is introduced into a film forming chamber equipped with a heatable substrate holding device and a vacuum exhaust device, and the tip of the nozzle is moved An ultrafine particle film forming portion disposed close to the surface of the substrate held by the substrate holding device, wherein an intermediate chamber provided with an oxygen gas introduction pipe is connected to a tip end of the transfer pipe.

Further, another forming apparatus comprises a plurality of evaporation sources for heating and evaporating a plurality of elements constituting the high-temperature superconducting material at a proportion of the composition of the high-temperature superconducting material to generate a mixture of ultrafine particles. In the particle generation chamber, an ultra-vacuum device for evacuating the chamber, an inert gas introduction pipe, and a transport pipe having a nozzle at the tip and connecting the generated ultra-fine particle mixture together with the inert gas are connected. A transport tube having a nozzle at the tip is guided into a film forming chamber equipped with a fine particle generator, a heatable substrate holding device and a vacuum exhaust device, and the tip of the nozzle approaches the substrate surface held by the substrate holding device. And an intermediate chamber provided with an oxygen gas introducing pipe is connected to the distal end side of the transport pipe.

(Function) The composition ratio of the high-temperature superconducting material is determined by co-evaporation or simultaneous evaporation of a plurality of elements constituting the high-temperature superconducting material by one or a plurality of evaporation sources provided in the ultrafine particle generation chamber. A mixture of ultrafine particles is generated by heating and evaporating as described above, and the mixture of ultrafine particles having such a predetermined composition is sprayed together with a carrier gas containing oxygen gas from a nozzle onto a heated substrate to deposit an ultrafine particle film on the substrate. Let it form.

(Example) An example of a forming method and an apparatus of the present invention will be described with reference to the accompanying drawings.

Figure 1, for example, except oxygen such as _{Bi 0.7 · Pb 0.3 · · Sr} 1 · Ca 1 · Cu 2 O Y -based superconductor thick film (hereinafter referred BPSCCO based film) 5 kinds of elements (Bi, Pb , Sr, Ca, Cu) shows an example of an apparatus for forming a thick film of a high-temperature superconductor composed of: (1) a first ultrafine particle generation chamber (hereinafter referred to as a first generation chamber); 2 Ultra-fine particle generation chamber (hereinafter referred to as a second generation chamber), 3 is an intermediate chamber, 4 is a film formation chamber, and the first generation chamber 1, the second generation chamber 2 and the film formation chamber 4 are vacuum pumps 5,
6, 7 are connected via exhaust pipes 8, 9, 10. 11,12,13
Denotes regulating valves intervening in the exhaust pipes 8, 9 and 10, respectively. The first generation chamber 1 and the second generation chamber 2 are connected to inert gas introduction pipes 16 and 17 having one ends connected to the cylinders 14 and 15 of the inert gas supply source via regulating valves 18 and 19, respectively. The intermediate chamber 3 and the film forming chamber 4 are connected to oxygen gas supply pipes 22 and 23 having one ends connected to cylinders 20 and 21 of an oxygen gas supply source via regulating valves 24 and 25, respectively. Further, the first production chamber 1 has a raw material A "for example, bismuth (Bi) and lead (P
b), a first evaporation source 28 comprising a container 26 made of a tantalum crucible and a heating device 27 for indirectly heating the container 26 with a tantalum heater or the like; The raw material B to be made, for example, strontium (S
r) and a second evaporation source 29 for “calcium (Ca)”. The second generation chamber 2 has the same structure as that of the first evaporation source 28 in the lower part, and the raw material C to be heated and evaporated, for example, copper (C
u) ”is provided with an evaporation source 30 including a graphite crucible-containing container 26 and a heating device 27 that indirectly heats the container 26 with a tantalum heater or the like. The container 26 and the heating device 27 can be appropriately selected from known ones according to the elemental material to be heated and evaporated. The film forming chamber 4 has, for example,
A moving device 33 for horizontally moving a substrate holding device 32 for holding a magnesia (MgO) substrate 31 having a square shape and a thickness of 1 mm. In addition, the moving device 33 includes a resistance heating device 34 that can freely heat the substrate 31.

Reference numeral 35 denotes a first transfer pipe having an opening at an upper part in the first generation chamber 1 and penetrating the ceiling part thereof in an airtight manner and leading to the outside.
Denotes a second transfer pipe having one end opened at the upper part in the second generation chamber 2 and penetrating the ceiling part thereof in an airtight manner and led out to the outside.
The first transfer pipe 35 is formed of, for example, a thin pipe having an inner diameter of 6 mm and an outer diameter of 7.2 mm. The other end is opened inside the intermediate chamber 3, and the main transfer pipe 37 is formed by airtightly penetrating one side wall of the intermediate chamber 3. I do. The second transfer pipe 36 is made of, for example, a small pipe having an inner diameter of 3.6 mm and an outer diameter of 4.8 mm, and the other end is inserted into the main transfer pipe 37 from the pipe wall to the inside to be airtightly connected. A concentric double tube portion 38 that opens toward the container is formed. In this case, the cross-sectional areas of the inner and outer passages in the double pipe portion 38 are both equal to 10 mm ² . Three
Reference numeral 9 denotes a transfer pipe having an opening at one end close to and opposed to the opening of the main transfer pipe 37 in the intermediate chamber 3, and airtightly penetrating the other side wall of the intermediate chamber 3 and leading to the outside. Nozzle 40, and airtightly penetrates the ceiling of the film forming chamber 4,
The tip of the nozzle 40 is spaced from the substrate 31 in the film forming chamber 4 by 1 mm. The nozzle 40 has a long diameter of 1 mm and a short diameter of 0.5 mm
Are arranged in such a manner that the axis of the minor axis is directed in the moving direction of the substrate 31.

 Next, the operation of the above-described first forming apparatus will be described.

A Bi-Pb alloy having a weight ratio of bismuth (Bi) 7: lead (Pb) 3 is prepared as the raw material A in the container 26 of the first evaporation source 28 in the first generation chamber 1, and A Sr-Ca alloy of strontium (Sr) 1: calcium (Ca) 1 is prepared as a raw material B in the container 26 of the second evaporation source 29, and the raw material B in the container 26 of the evaporation source 30 in the second generation chamber 2 is prepared. Copper (Cu) is prepared as a raw material C. While the vacuum pumps 5, 6 and 7 were operated, argon (Ar) gas was introduced into each of the production chambers 1 and 2 from the inert gas introduction pipes 16 and 17, respectively.
A, B and C are heated and evaporated. Table 3 shows the conditions for forming the ultrafine particles at this time.

Thus, Bi, Pb, Sr generated in the first generation chamber 1 and
The mixture of the Ba ultrafine particles and the Cu ultrafine particles generated in the second generation chamber 2 use the introduced inert gas as a carrier gas, and a pressure difference between the mixture and the film formation chamber 4 to make each transport pipe 35 , 3
6 and the main transfer pipe 37, the wafer is transferred to the film forming chamber 4 via the intermediate chamber 3, and the mixture of Bi and Pb is mixed near the opening of the transfer pipe 35 above the first generation chamber 1 during the transfer. Fine particles and S
The mixed ultrafine particles of r and Ca are mixed in an inert gas, and the mixture of the ultrafine particles of Bi, Pb, Sr, and Ca, and the ultrafine particles of Cu are mixed with the carrier gas near the opening of the double pipe section 38. Mix in inert gas. The mixture of the ultrafine particles of Bi, Pb, Sr, Ca and Cu flows in the main carrier pipe 37 together with the carrier gas and reaches the intermediate chamber 3 where the oxygen (O ₂ ) Since a gas of 0.2 l / min is introduced, O ₂ gas is added to the carrier gas from the intermediate chamber 3 to the film forming chamber 4, and oxidation of ultrafine particles of Bi, Pb, Sr, Ca, and Cu in the transfer pipe 39. Progresses.

The mixed ultrafine particles transported into the film forming chamber 4 through the transport pipe 39 are fed from the nozzle 40 at the tip thereof to the MgO substrate 31 having a side of 20 mm and a thickness of 1 mm, which is held by the substrate holding device 32 at an interval of 1 mm.
Injected on the surface. The substrate 31 is previously heated at 450 ° C.
Is moved by the moving device 33 in the direction of the minor axis of the nozzle 40 at a speed of 3 mm / min to form a continuous film.

During the film formation, the pressure and the amount of the inert gas introduced into each of the production chambers 1 and 2 shown in Table 3 were maintained, and 0.2 l / min of O ₂ gas was introduced into the intermediate chamber 3 while the film was heated at the time of film formation. 0.5 l / min from the oxygen gas introduction pipe 23 to the film formation chamber 4 to prevent oxygen deficiency
It has introduced the O ₂ gas. The pressure in the film forming chamber 4 is 2.4 Torr
The partial pressure of O ₂ gas is 0.5 Torr.

After the film is formed, the film forming chamber 4 is filled with oxygen gas to atmospheric pressure, and then the substrate 31 is gradually cooled from 450 ° C. to room temperature and then taken out.

The composition ratio of Bi, Pb, Sr, Ca and Cu in the formed BPSCCO diameter film was examined by X-ray microanalysis (X-ray microanalyzer), and the results are shown in Table 4.

As is clear from Table 4, the BPSC formed in the above example
It was confirmed that the composition ratio of Bi, Pb, Sr, Ca and Cu in the CO-based film reached the target value.

After the evaporation for forming the high-temperature superconducting film, the weight loss due to the evaporation of the Bi · Pb alloy and the Sr · Ca alloy was determined to be 152 mg and 85 mg, respectively.

The BPSCCO-based film formed by the above forming method was further subjected to a heat treatment at 850 ° C. for 20 hours in the air, and the RT characteristics at low temperature were measured. As a result, the critical temperature was Tc (on) 98K, Tc (off ) 80K
, And the measurement results by X-ray diffraction showed a C-axis oriented high temperature superconducting crystal.

Although the BPSCCO-based film has been described in the first illustrated embodiment, the present invention is not limited to this. For example, the raw material A put in the vessel 26 of the first evaporation source 28 in the first generation chamber 1 is Bi-Pb
An element such as ytterbium (Yb) alone instead of the alloy, or a raw material B put in the container 26 of the second evaporation source 29 in the same chamber 1 is replaced with an element such as barium (Ba) alone instead of the Sr-Ca alloy, A film of a high-temperature superconducting material composed of three elements such as Yb, Ba, Cu, and O, excluding oxygen, using a Cu element as a raw material C to be put into a container 26 of an evaporation source 30 in a second generation chamber 2 Widely applicable to formation.

Figure 2, for example _{Y 1 · Ba 2 · Cu 3} · O 7-X based oxygen except three elements such as high-temperature superconductor thick film (hereinafter referred to as YBCO-based film) (Y, Ba, Cu) from This shows one example of an apparatus for forming a thick film of a high-temperature superconductor formed, in which 51 is a first ultrafine particle generation chamber (hereinafter, referred to as a first generation chamber), and 52 is a second ultrafine particle generation chamber (hereinafter, a first generation chamber). Reference numeral 53 denotes an intermediate chamber, 54 denotes a film formation chamber, and a first generation chamber 51, a second generation chamber 52, and a film formation chamber.
Numeral 54 is connected to vacuum pumps via exhaust pipes 58, 59, 60, respectively. Reference numerals 61, 62 and 63 denote control valves intervening in the exhaust pipes 58, 59 and 60, respectively. Further, the first generation chamber 51 and the second generation chamber 52 are connected via control valves 68 and 69 to inert gas introduction pipes 66 and 67 having one ends connected to cylinders 64 and 65 of an inert gas supply source, respectively. The intermediate chamber 53 and the film forming chamber 54 are provided with oxygen gas introduction pipes 72 and 73 having one ends connected to cylinders 70 and 71 of an oxygen gas supply source via control valves 74 and 75, respectively. Furthermore, the first
The lower part of the production chamber 51 is provided with an evaporation source 78 composed of a container 76 made of a tantalum crucible for accommodating a raw material A to be heated and evaporated, for example, barium (Ba), and a heating device 77 for indirectly heating this with a tantalum heater or the like. . The second generation chamber 52 is heated by an arc discharge between a tungsten electrode and a container 79 made of a water-cooled copper hearth or the like containing a raw material B (for example, yttrium (Y) and copper (Cu)) to be heated and evaporated at a lower portion thereof. And an evaporation source 81 consisting of 80. The containers 76 and 79 and the heating devices 77 and 80 of these evaporation sources 78 and 81 can be appropriately selected from known ones according to the element materials to be heated and evaporated. The film forming chamber 54 is provided with, for example, a magnesium (MgO) substrate 82 having a square shape of 20 mm on a side and a thickness of 1 mm, and a moving device 84 for horizontally moving a substrate holding device 83 for holding the substrate 82. Further, the moving device 84 includes a resistance heating and heating device 85 that can freely heat the substrate 82.

Reference numeral 86 denotes a first transfer pipe having one end opened at an upper part in the first generation chamber 51 and penetrating the ceiling part thereof in an air-tight manner and led out to the outside.
Denotes a second transfer pipe having one end opened at the upper part in the second generation chamber 52, penetrating the ceiling part thereof airtightly, and leading to the outside.
The first transfer pipe 86 is formed of, for example, a thin tube having an inner diameter of 6 mm and an outer diameter of 7.2 mm, and has another end opened inside the intermediate chamber 53 and hermetically penetrating one side wall of the intermediate chamber 53 to form a main transfer pipe 88. I do. The second
The transfer pipe 87 is formed of, for example, a thin tube having an inner diameter of 3.6 mm and an outer diameter of 5.4 mm, and the other end is inserted into the main transfer pipe 88 from the wall thereof to be airtightly connected, and is opened toward the intermediate chamber 53. A concentric double pipe section 89 is formed. In this case, the cross-sectional areas of the inner and outer passages in the double pipe portion 89 are both equal to 10 mm ² . Reference numeral 90 denotes a transfer pipe whose one end opening is close to and opposed to the opening of the main transfer pipe 88 in the intermediate chamber 53, penetrates the other side wall of the intermediate chamber 53 in an airtight manner, and is provided to the outside. A nozzle 91 is formed, and the ceiling of the film forming chamber 54 is airtightly penetrated. The tip of the nozzle 91 has a gap of 1 mm from the substrate 82 in the film forming chamber 54. The nozzle 91 has an elliptical shape with a major axis of 1 mm and a minor axis of 0.5 mm, and is arranged with the minor axis oriented in the moving direction of the substrate 82.

 Next, the operation of the forming apparatus shown in FIG. 2 will be described.

Barium (Ba) is prepared as a raw material A in the container 76 of the evaporation source 78 in the first generation chamber 51, and yttrium (Y) is used as a raw material B in the container 79 of the evaporation source 81 in the second generation chamber 52. 2.5:
A Y (Cu) alloy of copper (Cu) 1 is prepared. Vacuum pump 55, 56
And 57, while the inert gas introduction pipes 66 and 67
Helium (He) gas is introduced into each of the production chambers 51 and 52, and the raw materials A and B are heated and evaporated by the heating devices 77 and 79, respectively. Table 5 shows the conditions for forming the ultrafine particles at this time.

Thus, the ultrafine particles of Ba generated in the first generation chamber 51 and the ultrafine particles of the mixture of Y and Cu generated in the second generation chamber 52 use the introduced inert gas as a carrier gas, respectively.
Due to the pressure difference between the film forming chamber 54 and each of the transfer pipes 86 and 87 and the main transfer pipe 8
8, the mixture is conveyed to the film formation chamber 54 via the intermediate chamber 53, and in the main conveyance pipe 88 in the middle of conveyance, a mixture of ultrafine particles of Y and Cu and Ba The fine particles are mixed with the carrier gas in an inert gas. This mixture of ultrafine particles of Y, Cu and Ba together with the carrier gas
After flowing through the inside 88 and reaching the intermediate chamber 53, oxygen (O ₂ ) gas 0.2 l / min is introduced from the oxygen gas introduction pipe 72 in the intermediate chamber 53, so that the carrier gas from the intermediate chamber 53 to the film forming chamber 54. O ₂ gas is added to the inside, and the oxidation of ultrafine particles of Y, Cu and Ba proceeds in the transport tube 90.

The mixed ultrafine particles transported into the film forming chamber 54 through the transport pipe 90 are maintained on the MgO substrate 82 having a side length of 20 mm and a thickness of 1 mm held by the substrate holding device 83 while maintaining a gap of 1 mm from the nozzle 91 at the tip. Injected to The substrate 82 is heated in advance to a temperature of 450 ° C. by the heating device 85, and is moved by the moving device 84 in the direction of the minor axis of the nozzle 91 at a speed of 3 mm / min to form a continuous film.

During the film formation, the pressure and the amount of the inert gas introduced into each of the production chambers 51 and 52 shown in Table 5 were maintained, and 0.2 l / min of O ₂ gas was introduced into the intermediate chamber 53. 0.5 l / m from the oxygen gas introduction pipe 73 to the film formation chamber 54 to prevent oxygen deficiency
In O ₂ gas is introduced. The pressure of the film forming chamber 54 is 3.8 Torr
At r, the partial pressure of the O ₂ gas is 0.7 Torr.

After forming the film, the film forming chamber 54 is filled with O ₂ gas to the atmospheric pressure, and then the substrate 82 is gradually cooled from 450 ° C. to room temperature, and then taken out.

The composition ratio of Y, Cu and Ba in the formed YBCO-based thick film is changed to X
Inspection was conducted by X-ray microanalysis (X-ray microanalyzer), and the results are shown in Table 6.

As is clear from Table 6, the YBCO formed in the above example was
It was confirmed that the composition ratio of Y, Cu and Ba in the base film reached the target value.

In the second embodiment, the raw material B to be filled in the container 79 of the evaporation source 81 was prepared as follows. First, the element Y17g and Cu6.8g (weight ratio: Y: Cu = 2.5: 1) as the raw material B are put in a water-cooled copper hearth, and a direct current arc discharge (10V × 240A) is applied between the chip-shaped W electrode. This was melted to form a button-shaped mother alloy.

The amount of weight loss due to evaporation of the Y-Cu alloy after evaporation for forming a high-temperature superconducting film was 180 mg.

The temperature of the YBCO-based film formed by
As a result of performing heat treatment at 900 ° C. for 3 hours and measuring RT characteristics at a low temperature, the critical temperatures are Tc (on) 90 K, Tc (off) 80 K
, And the measurement results by X-ray diffraction showed a C-axis oriented high temperature superconducting crystal.

In the second embodiment, the YBCO-based thick film is described. However, the present invention is not limited to this, and can be widely applied to other high-temperature superconducting materials.

In addition, according to the forming method of the first illustrated embodiment and the second illustrated embodiment, the film has a width of 0.05 to 10 mm and a thickness of 1 to 1 by appropriately selecting the diameter of the nozzle and the moving speed of the substrate. Although a range of 1000 μm is formed, this value is not a limit of the forming method of the present invention. For the length, for example, a long continuous film can be formed by a single-stroke method,
The thickness can be increased by, for example, lamination.

In addition, in the method of the present invention, for example, a barium titanate (BaTiO ₃ ) film is formed as a material having a high dielectric constant by using a gas deposition method as a material having a high dielectric constant. Sr, Ca and Z to improve their properties
Since the addition of rO ₂ is effective in moving the Curie temperature to around the normal temperature and flattening the temperature change of the dielectric constant, the addition of Sr, Ca and ZrO ₂ into the BaTiO ₃ film causes the evaporation source of the device of the present invention. It is possible by using.

(Effect of the Invention) As described above, according to the present invention, the ratio of the composition of the high-temperature superconducting material to one or a plurality of evaporation sources provided in the ultrafine particle generation chamber is determined by the composition of the high-temperature superconducting material. Heat to produce a mixture of ultrafine particles,
Since a mixture of these ultrafine particles is transported by a carrier gas, an oxygen gas is added to the carrier gas, and the mixture is sprayed onto a heated substrate to form an ultrafine particle film. A superfine particle mixture having a uniform composition can be obtained by co-evaporation or co-evaporation without heating and evaporating each element of the superconducting material. Since there is no need to install auxiliary equipment such as a vacuum exhaust device for each production chamber, an inert gas introduction pipe, and a transport pipe for the generated ultrafine particles, the apparatus is simple, and a large number of ultrafine particles are required. There is an effect that the installation of the apparatus can be made small in area without the need for a production chamber.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of one embodiment of the device of the present invention, FIG. 2 is an explanatory diagram of another embodiment, and FIG. 3 is an explanatory diagram of a conventional device. 1,51: first ultra-fine particle generation chamber 2,52 ... second ultra-fine particle generation chamber 3,53 ... intermediate chamber 4,54 ... ultra-fine particle film formation chamber 5,6,7,55,56,57 ... vacuum exhaust device 8,9,58,59… Inert gas introduction pipe 31,82… Substrate 32,83… Substrate holding device 35,86… First transport pipe 36,87… Second transport pipe 37,88… Main transport pipe 39, 90… Conveyer tube 40,91… Nozzle

Claims (6)

(57) [Claims] An ultra-fine particle obtained by heating and evaporating a plurality of elements constituting a high-temperature superconducting material so as to have a composition ratio of the high-temperature superconducting material by a single evaporation source in an ultra-fine particle generation chamber in an inert gas atmosphere. Oxygen gas is introduced into the carrier gas while transporting the mixture of ultrafine particles using the inert gas as a carrier gas, and the mixture of ultrafine particles is passed through a nozzle together with a carrier gas containing oxygen gas from a nozzle. A method for forming a high-temperature superconductor thick film, which comprises spraying an ultrafine particle film on a heated substrate to form an ultrafine particle film on the substrate. 2. A method in which a plurality of elements constituting a high-temperature superconducting material are heated and evaporated by a plurality of evaporation sources in an ultrafine particle generation chamber in an inert gas atmosphere so as to have a composition ratio of the high-temperature superconducting material. Oxygen gas is introduced into the carrier gas while the mixture of ultrafine particles is generated as a carrier gas using the inert gas as a carrier gas, and the mixture of ultrafine particles is mixed with a carrier gas containing oxygen gas by a nozzle. Forming a high-temperature superconductor thick film by spraying onto a substrate heated from above to form an ultrafine particle film on the substrate. 3. One of the elements constituting the high-temperature superconducting material is generated in a separate ultra-fine particle generation chamber, and the ultra-high-temperature superconducting material is formed by evaporating it to a composition ratio of the high-temperature superconducting material. 3. The method for forming a high-temperature superconductor thick film according to claim 1, wherein the high-temperature superconductor thick film is mixed with a mixture of fine particles and transported. 4. An ultrafine particle generation chamber having one evaporation source for simultaneously heating and evaporating a plurality of elements constituting the high-temperature superconducting material in a proportion of the composition of the high-temperature superconductive material to generate a mixture of ultrafine particles. An ultra-fine particle generating unit in which a vacuum exhaust device for evacuating the room, an inert gas introduction pipe, and a transport pipe having a nozzle at the tip and leading out a mixture of generated ultra-fine particles together with the inert gas are connected. And guiding a transfer pipe having a nozzle at the tip into a film forming chamber equipped with a freely heatable substrate holding device and a vacuum exhaust device, and disposing the tip of the nozzle close to the substrate surface held by the substrate holding device. A high-temperature superconductor thick film forming apparatus, comprising: an intermediate chamber having an oxygen gas introduction pipe connected to a tip side of the transfer pipe. 5. An ultrafine particle generation chamber having a plurality of evaporation sources for heating and evaporating a plurality of elements constituting the high-temperature superconducting material in proportion to the composition of the high-temperature superconductive material to generate a mixture of ultrafine particles. An ultra-fine particle generating unit connected to a vacuum exhaust device for evacuating the room, an inert gas introduction pipe, and a transport pipe having a nozzle at the tip and leading out a mixture of generated ultra-fine particles together with the inert gas. A transport pipe having a nozzle at the tip was guided into a film forming chamber equipped with a freely heatable substrate holding device and a vacuum exhaust device, and the tip of the nozzle was arranged close to a substrate surface held by the substrate holding device. An apparatus for forming a high-temperature superconductor thick film, comprising: an ultrafine particle film forming section; and an intermediate chamber provided with an oxygen gas introducing pipe connected to a tip side of the transfer pipe. 6. A vacuum evacuation apparatus for evacuating a room in an ultrafine particle generation chamber provided with an evaporation source for separately heating and evaporating one of the elements constituting the high-temperature superconducting material to generate ultrafine particles. And an inert gas introduction pipe, and a transport pipe that guides the generated ultrafine particles together with the inert gas, wherein the transport pipe of the ultrafine particle generation unit is coupled to the transport pipe on the upstream side of the intermediate chamber. The apparatus for forming a high-temperature superconductor thick film according to claim 4 or 5, wherein: