WO2021221238A1 - Apparatus and method for manufacturing high temperature superconductor - Google Patents

Abstract

An apparatus for manufacturing a high temperature superconductor, according to the present invention, comprises: a vacuum chamber; a plurality of deposition spaces partitioned by a partition member for each of deposition materials provided inside the vacuum chamber; a guide drum which is formed with a length that passes through all of the plurality of deposition spaces inside the vacuum chamber, and which has, on the outer surface thereof, a guide groove for guiding the movement of a substrate; a supply reel provided inside the vacuum chamber at one side of the guide drum so as to supply the substrate along the guide groove; and a collection reel provided inside the vacuum chamber at the other side of the guide drum so as to collect the substrate having passed through all of the plurality of deposition spaces, wherein the partition member comprises: a lower partition member which forms a vacuum chamber and which prevents the inflow of each deposition material into another space in a lower chamber that provides the evaporation space of the deposition materials; and an upper partition member which forms the vacuum chamber and which partitions an upper chamber, providing the reaction space of a material deposited on the substrate, so that same corresponds to a partitioned position of the lower chamber, and one surface of each of the upper partition member and the lower partition member is formed to correspond to the outer surface shape of the drum.

Description

High-temperature superconducting wire rod manufacturing apparatus and method

The present invention relates to an apparatus and method for manufacturing a high-temperature superconducting wire for manufacturing a high-temperature superconducting wire by depositing a material layer by at least one of electron beam evaporation, sputtering, and thermal evaporation while supplying a substrate in a reel-to-reel method.

The superconducting phenomenon is a physical phenomenon in which the resistance of a material approaches zero below a critical temperature. It has excellent properties. Such characteristics of the superconducting wire can improve product performance as well as realize miniaturization.

Therefore, superconducting wire rods are used in various industrial fields, such as the development of power devices such as superconducting magnets, superconducting cables, superconducting motors and superconducting generators, as well as medical equipment such as NMR and MRI, and large scientific equipment such as accelerators and nuclear fusion devices. Consistent efforts are being made to do this.

Meanwhile, the superconducting wire is divided into a low temperature superconductor (LTS) and a high temperature superconductor (HTS) based on a critical temperature.

Among them, high-temperature superconducting wire (HTS) has a critical temperature of 100K (-173°C) compared to low-temperature superconducting wire (LTS) with a critical temperature close to absolute 0K (-273 ℃), showing superconducting properties at a relatively high temperature. , is mainly manufactured and utilized in thin film type.

And, in the case of a high-temperature superconducting wire manufactured in a thin film type, the higher the critical current is, the better the crystals of the superconducting thin film are aligned. Accordingly, various efforts are being made to improve crystal orientation in order to secure a high critical current of the superconducting layer.

In the case of the currently commercialized high-temperature superconducting wire, a physical vapor deposition (PVD) method is used on a metal substrate in the form of a biaxially-oriented tape, and the manufacturing process is multi-step, which is uneconomical.

First, in order to manufacture a high-temperature superconducting thin-film wire having excellent properties, a metal substrate in the form of a tape used must have biaxial orientation.

The two-axis-oriented metal substrate manufacturing method is typically divided into Rolling Assisted Biaxially Textured Substrate (RABiTS) and Ion Beam Assisted Deposition (IBAD) method. do.

A plurality of buffer layers are epitaxially formed along the crystal orientation on the tape-shaped biaxially-oriented metal substrate manufactured by the above method, and a high-temperature superconducting layer is deposited on the buffer layer.

In detail, the buffer layer is formed by pulsed laser deposition, RF-Sputtering, thermal co-evaporation, metal organic chemical vapor deposition, or metal organic chemical vapor deposition. Organic Deposition) and the like may be deposited.

Also, in the case of the high-temperature superconducting layer, it is deposited by PLD (Pulsed Laserdeposition), RF-Sputtering, Thermal Co-evaporation, MOCVD (Metal Organic Chemical Vapor Deposition), or MOD (Metal Organic Deposition) method, etc., and the upper side of the high-temperature superconducting wire is By further forming a protective layer and a stabilizing layer again, the production of the high-temperature superconducting wire is completed.

For example, in Korean Patent Registration No. 1093085, “Method and apparatus for forming a superconducting material on a tape substrate,” a number of vacuum chambers corresponding to each process are arranged in series to communicate with each other, and supply and recovery of the tape substrate at both ends A high-temperature superconducting wire is manufactured by sequentially depositing and heat-treating it through a chamber corresponding to each process, including a reel chamber having a reel for each.

However, in the above case, the number of vacuum chambers corresponding to each manufacturing process is required, and since separation chambers for separating the chambers must be additionally included, there is a problem in that the manufacturing cost is increased.

In addition, as each chamber is arranged in series, it is difficult to secure a space for the installation of the high-temperature superconducting wire rod manufacturing apparatus. I have a problem with having to place it.

It is an object of the present invention to provide an apparatus for manufacturing a high-temperature superconducting wire rod capable of varying the internal space of a vacuum chamber according to the type and quantity of material layers to be deposited while simplifying the manufacturing process.

Another object of the present invention is to provide an apparatus for manufacturing a high-temperature superconducting wire rod that improves crystal orientation even when a polycrystalline substrate is used so that a high-temperature superconducting layer can be deposited.

It is an object of the present invention to provide a method for manufacturing a high-temperature superconducting wire rod for manufacturing a high-temperature superconducting wire in which a single-crystal level superconducting layer is formed using the high-temperature superconducting wire rod manufacturing apparatus for the above purpose.

The apparatus for manufacturing a high-temperature superconducting wire according to the present invention includes a vacuum chamber, a plurality of deposition spaces partitioned by a partition member for each deposition material provided in the vacuum chamber, and all of the plurality of deposition spaces inside the vacuum chamber. a guide drum having a length and having a guide groove formed on an outer surface thereof for guiding the movement of the substrate, and a supply reel provided at one side of the guide drum inside the vacuum chamber to supply the substrate along the guide groove; and a recovery reel provided on the other side of the guide drum inside the vacuum chamber to recover the substrates passing through all of the plurality of deposition spaces, the partition member constituting the vacuum chamber and a lower chamber providing an evaporation space for the deposition material a lower partition member for preventing the inflow of each deposition material into another space; It is configured to include, and each one surface of the upper partition member and the lower partition member is characterized in that it is formed to correspond to the shape of the outer surface of the drum.

It is characterized in that the deposition material accommodated in the deposition space includes a material having a crystal orientation of a single crystal level by satisfying [Relational Equation A].

[Relational A]

0°< FWHM2 ≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)

The lower and upper chambers are provided with lower fixing means and upper fixing means arranged at equal intervals along the longitudinal direction of the guide drum, respectively, and the lower and upper partition members are fixed to the lower part according to the required space. It is characterized in that it is fitted while changing the position of the means and the upper fixing means.

In another aspect, the method for manufacturing a high-temperature superconducting wire according to the present invention includes a guide drum preparation step including a guide drum for transferring a substrate in a reel-to-reel method inside a vacuum chamber, and deposition deposited on the guide drum inside the vacuum chamber. A lower chamber partitioning step of disposing a material and partitioning each deposition material arrangement space using a lower partition member, and an upper chamber partitioning step of partitioning an upper chamber inner space using an upper partition member to correspond to the lower chamber partitioning step and a deposition step of sequentially depositing a deposition material while rotating a guide drum in a vacuum chamber in which an internal space is partitioned.

In the lower chamber partitioning step, when the deposition material is disposed, a material having a single crystal level of crystal orientation is disposed in front of the arrangement space of the material forming the superconducting layer by satisfying [Relational Expression A].

[Relational A]

0°< FWHM2 ≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)

The deposition step of yttrium oxide to the substrate in the compartment the first space (Y ₂ O ₃₎ to the first deposition step of depositing, the yttrium oxide in the compartment second space (Y ₂ O ₃₎ is IBAD on the deposited substrate In the second deposition process of depositing magnesium oxide (MgO) in this way, and in the partitioned third space, a material having a single crystal level of crystal orientation is deposited by satisfying [Relational A] on the substrate on which the magnesium oxide (MgO) layer is deposited. The third deposition process in which the orientation deposition of single crystal level is performed and the fourth deposition process of depositing the superconducting layer using the simultaneous thermal evaporation method on the upper side of the crystal orientation improvement material layer oriented and deposited at the single crystal level in the divided fourth space And, a fifth deposition process of forming a protective layer by depositing silver (Ag) on the upper side of the superconducting layer in the partitioned fifth space, and the fifth deposition process in the partitioned sixth space. and then a sixth process of controlling the oxygen composition ratio of the superconducting layer by supplying oxygen into the sixth space.

[Relational A]

0°< FWHM2 ≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)

According to the present invention, a receiving space for each deposition material is partitioned inside the vacuum chamber, and the deposition material for each section is sequentially stacked while the substrate supplied and recovered in a reel-to-reel method is rotated along the guide groove formed in the drum. can

Accordingly, a plurality of vacuum chambers are not required, and a continuous stacked structure can be easily formed through a single preparation process, thereby reducing the time and cost required for manufacturing the high-temperature superconducting wire.

In addition, according to the present invention, a space in which the crystal orientation improving material is accommodated is provided in the deposition material provided inside the vacuum chamber, and the material and the superconducting layer are subsequently deposited after the crystal orientation improving material is deposited prior to the deposition of the superconducting material. A high-temperature superconducting wire having a single-crystal-level superconducting layer having improved crystal orientation even on a polycrystalline substrate by epitaxial deposition can be manufactured.

In addition, in the case of adding another functional layer to the buffer layer or reducing the type of the buffer layer, and in the case of forming the protective layer and the stabilization layer after the formation of the superconducting layer, the internal space of the vacuum chamber can be easily partitioned using a partition member. Since it can be changed, it is easy to improve the process and has the advantage of reducing the manufacturing cost required for process improvement.

1 is a view for showing the main configuration of a high-temperature superconducting wire rod manufacturing apparatus according to the present invention.

Figure 2 is a view showing the installation structure of the partition member as a main part of the present invention.

3 is a view for explaining the internal space partition structure of the apparatus for manufacturing a high-temperature superconducting wire according to the present invention;

4 is a view showing an embodiment of an upper chamber partition member (a) and a lower chamber partition member (b), which are essential parts of the present invention.

5 is a view showing an embodiment of a horizontal partition member as a main part of the present invention.

6 is a view showing an embodiment of the partitioned inner space of the high-temperature superconducting wire manufacturing apparatus according to the present invention.

7 is a view for showing a process of manufacturing a high-temperature superconducting wire using the high-temperature superconducting wire manufacturing apparatus according to the present invention.

8 is a view for showing a single crystal formation mechanism of the present invention.

9 is a view showing a FeCo thin film as a crystal orientation improving material according to a preferred embodiment of the present invention.

10 is a graph showing the analysis of 2-theta according to the composition ratio of the thin film formed of _{Fe x} Co _1-x alloy according to an embodiment of the present invention;

11 is a view showing the alignment of crystals in the plane direction by analyzing Phi Scan by applying MgO and LMO as a polycrystalline buffer material according to an embodiment of the present invention.

12 is a view showing the crystal orientation ability according to the half width of the crystal orientation difference angle of the crystal grains at the grain boundary of the polycrystalline buffer material according to an embodiment of the present invention.

13 is a view showing the crystal orientation ability according to the deposition rate of the crystal orientation improving material by the thermal evaporation method according to an embodiment of the present invention.

14 is a view showing the crystal orientation ability according to the deposition temperature in the step of forming a thin film by depositing a crystal orientation improving material by a thermal evaporation method according to an embodiment of the present invention.

15 is a view showing the experimental results for the thickness showing the crystal orientation of the single crystal level.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. In adding reference numerals to components in each drawing, the same components are denoted by the same reference numerals as much as possible even though they are indicated in different drawings. described. In addition, in the description of the embodiment, if it is determined that a detailed description of a related known configuration or function interferes with the understanding of the embodiment of the present invention, the description is simplified or omitted, and a certain element is located above another element. When it is described as “having”, “laminated”, “deposited” or “formed”, the component may be provided, laminated, deposited, or formed directly on the top surface of the other component, but another component may be formed between each component. It should be understood that a component may be “prepared,” “laminated,” “deposited,” or “formed.”

The high-temperature superconducting wire manufacturing apparatus according to the present invention is configured to manufacture a high-temperature superconducting wire by sequentially depositing deposition materials according to the movement position of the substrate while the substrate is transferred in a reel-to-reel manner in a vacuum chamber.

Hereinafter, the present invention having the above functions will be described in more detail with reference to the accompanying drawings.

1 is a view showing the main configuration of the apparatus for manufacturing a high-temperature superconducting wire according to the present invention, FIG. 2 is a view showing the installation structure of the partition member, which is the main part of the present invention, and FIG. 3 is the present invention. A drawing for explaining the internal space partition structure of the high-temperature superconducting wire rod manufacturing apparatus according to the present invention is shown.

Referring to these drawings, the apparatus for manufacturing a high-temperature superconducting wire according to the present invention rotates the guide drum 400 inside the vacuum chamber 200, along the guide groove (reference numeral not assigned) formed in the guide drum 400 . It is configured to continuously deposit a deposition material on the transferred substrate 100 .

In detail, the vacuum chamber 200 includes an upper chamber 220 , a lower chamber 260 , and a differential pressure chamber 240 , and the differential pressure chamber 240 is disposed between the upper chamber 220 and the lower chamber 260 . It is provided in the chamber to differential pressure exhaust the reaction gas generated in each chamber.

The upper chamber 220 maintains a relatively low vacuum state as oxygen and a reaction gas are supplied through the oxygen supply unit 500 . In addition, the deposition material deposited on the substrate 100 is heated and diffused by the heater to provide a reaction space for crystal growth, and an internal heater 420 and an external heater 222 are provided centering on the guide drum 400 . is provided to heat the reaction space.

The lower chamber 260 maintains a relatively high vacuum state, and supplies the deposition material so that the deposition material can be deposited on the substrate 100 .

In addition, the differential pressure chamber 240 maintains the lower chamber 260 in a high vacuum state through differential pressure exhaust that interworks with each other between the upper chamber 220 and the lower chamber 260 to clearly separate deposition and crystal growth environments. make it possible

The above-described guide drum 400 is provided inside the vacuum chamber 200 in an environment in which deposition and crystal growth environments are separated as described above.

The guide drum 400 further includes a supply reel 420 for supplying the substrate 100 and a recovery reel 440 for recovering the deposition-completed substrate 100, and guide grooves (not shown) along the outer circumferential surface. ) is formed.

The guide groove (not shown) has a width corresponding to the width of the supplied substrate 100 and is recessed to a predetermined depth inward from the outer circumferential surface of the guide drum 400 , and is formed in a spiral shape advancing toward the recovery reel 440 . .

Accordingly, the substrate 100 released from the supply reel 420 may be transferred in the direction of the recovery reel 440 along the guide groove at a constant speed by the rotation of the guide drum 400 while being accommodated in the guide groove.

On the other hand, in the supply structure as described above, since the substrate 100 may come into contact with the guide groove to generate contact resistance, various structures for preventing this may be applied.

As an example, the guide drum 400 uses a weight exposed by gravity to the outside of the guide groove according to the rotation of the drum as in “(Patent Document 2) KR10-0795065 B1” described in the prior art document of the present invention. Thus, a structure that reduces friction between the substrate and the guide groove may be applied.

As another example, the guide drum 400 is provided with a separate slip roller along the longitudinal direction of the drum as in “(Patent Document 3) KR10-0750654 B1” to reduce the friction of the substrate moving along the guide groove. can

In addition, the guide drum 400 according to the present invention is formed with a length passing through all of the accommodating space of the deposition material provided in the lower chamber 260 .

That is, in the apparatus for manufacturing a high-temperature superconducting wire according to the present invention, a plurality of deposition materials deposited on the substrate 100 are sequentially disposed inside the vacuum chamber 200 , and the deposition sequence according to the movement position of the substrate 100 . This is characterized in that it proceeds continuously so that a plurality of deposition processes can be performed through only one preparation process.

To this end, in the vacuum chamber 200 according to the present invention, a plurality of deposition materials are sequentially arranged in a space partitioned by partition members along the longitudinal direction of the guide drum 400 .

The partition member includes a lower partition member 800 that partitions the inner space of the lower chamber 260 in a direction in which a deposition material is supplied toward the substrate 100, and a lower partition member 800 that divides the inner space of the upper chamber 220 into the lower partition member ( The horizontal partition member 700 is provided in parallel with the axial direction of the upper partitioning member 600 and the guide drum 400 to partition to correspond to the position of 800) and positioned between the upper chamber 220 and the lower chamber 260. ) are separated.

In detail, FIG. 4 is a view showing an embodiment of the upper chamber partition member (a) and the lower chamber partition member (b), which are the main parts of the present invention, and FIG. 5 shows the horizontal partition member that is the main part of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS A drawing showing one embodiment is shown.

Referring to FIG. 5 first, the horizontal partition member 700 is a flat plate-shaped horizontal partition panel 720 that is formed longer than the length of the guide drum 400, and an opening 740 is formed in the central part, and the width is It is formed to correspond to the inside of the vacuum chamber 200 .

In addition, the opening 740 has a width smaller than the diameter of the guide drum 400 and is formed to have a length corresponding to the length of the guide drum 400 . Accordingly, when the horizontal partition member 700 is installed in a state in which the guide drum 400 is provided inside the vacuum chamber 200 , only a lower portion of the guide drum 400 is exposed toward the lower chamber 260 and the remaining The part should be shielded.

On the other hand, the upper partition member 600 shown in (a) of FIG. 4 is a flat upper partition panel 620 having a height and width corresponding to the height and width of the upper chamber 220, and the guide drum ( 400) and includes a drum upper accommodating portion 640 that is an opening having a shape corresponding to the upper portion.

And, the lower partition member 800 shown in (b) of FIG. 4 has a flat lower partition panel 820 having a height and width corresponding to the height and width of the lower chamber 260 and the guide drum ( 400), except for the shape of the upper drum accommodating part 640, includes a lower drum accommodating part 840 that is an opening having a shape corresponding to the lower shape of the guide drum 400.

That is, the upper partitioning member 600, the lower partitioning member 800, and the horizontal partitioning member 700 are the remaining vacuum chamber 200 except for the position where the guide drum 400 is provided outside the guide drum 400. It is formed in a shape corresponding to the inner space, and is installed so as not to contact the guide drum 400 so that the inner space of the vacuum chamber 200 can be divided into a plurality of partitioned spaces.

To this end, the lower chamber 260 and the upper chamber 220 are individually separated by the partition member as described above as the exhaust pumping for forming a vacuum environment as well as the exhaust pumping by the differential pressure chamber 220 are performed together. The space to be used may act as a deposition space and a reaction space of a region in which the corresponding deposition material is accommodated, respectively.

In addition, the partition member according to the present invention is installed to form an opening of 10 mm or less with the outer surface of the guide drum 400, so that the vacuum difference between the upper chamber 220 and the lower chamber 260 can be maintained.

For the installation structure as described above, a fixing means for installing the partition member is further provided inside the vacuum chamber 200 .

In detail, the horizontal partition member 700 may be fixedly installed on the horizontal fixing means 250 provided on the inner wall of the vacuum chamber 200 .

The horizontal fixing means 250 is formed in the form of a pair of protrusions having a distance spaced apart by the thickness of the horizontal partition panel 720 so that both ends of the front and rear sides of the horizontal partition panel 720 can be fitted respectively. can

The lower partition member 800 may be fixedly installed by a lower fixing means 270 provided on the bottom surface of the lower chamber 260 .

The lower fixing means 270 is a plurality of protrusions that are formed to protrude upward along the longitudinal direction of the guide drum 400, and the distance between the protrusions is formed by a distance corresponding to the thickness of the lower fixing panel 820 . do. Accordingly, the lower partition member 800 can be moved and installed at a desired position, and the installation position and quantity can be easily changed according to the quantity and the deposition range of the deposition material.

In addition, the upper partition member 600 may be fixedly installed by the upper fixing means 230 provided on the upper surface of the upper chamber 220 .

The upper fixing means 230 is formed at a position corresponding to the lower fixing means 270 to correspond to the installation position of the lower partition member 800 so that the upper partition member 600 can be fixedly installed.

Accordingly, the upper partition member 600 and the lower partition member 800 divide the inner space of the vacuum chamber 200 in a direction crossing the axial direction of the guide drum 400 so that one deposition material is separated from another deposition space. to be deposited and reacted.

Meanwhile, in the deposition space divided as described above, depending on the characteristics of the deposition material, E-beam evaporation, sputtering, thermal evaporator, and evaporation using Drun in Dual Chamber, EDDC ), the deposition can be made using one of the methods.

For example, in the deposition space where the superconducting layer is formed, Sm, Ba, and Cu, which are materials forming the superconducting layer, are co-evaporated by the EDDC method, and for this purpose, a crucible 280 in which each material is accommodated. And QCM (Quartz crystal microbalances) sensor for controlling the evaporation rate for each material may be provided.

6 is a view showing an embodiment of the partitioned inner space of the high-temperature superconducting wire rod manufacturing apparatus according to the present invention. And, FIG. 7 is a view showing a process of manufacturing a high-temperature superconducting wire using the high-temperature superconducting wire manufacturing apparatus according to the present invention.

Referring to these drawings, the method of manufacturing a high-temperature superconducting wire using the apparatus for manufacturing a high-temperature superconducting wire according to the present embodiment starts with the guide drum preparation step of installing the guide drum 400 inside the vacuum chamber 200. is carried out

In the guide drum preparation step, the guide drum 400 for transferring the substrate 100 while rotating together with the supply reel 420 and the recovery reel 440 at a constant speed is installed. The guide drum 400 is connected to a rotation motor from the outside so that the rotation speed can be varied, and a horizontal partition member 700 is installed between the upper chamber 220 and the lower chamber 260 to provide a guide drum 400 . Only a lower portion of the lower chamber 260 may be exposed above the lower chamber 260 .

After the guide drum 400 is installed, the deposition material deposited on the guide drum 400 is disposed inside the vacuum chamber 200, and each arrangement space is partitioned using the lower partition member 800. A partitioning step of the lower chamber. is performed

In the lower chamber partitioning step, the inner space of the lower chamber 260 is partitioned into a plurality of spaces in a direction crossing the axial direction of the guide drum 400, and in this embodiment, the lower chamber 260 has five lower partitions. It is divided into six spaced spaces by the member 800 .

Hereinafter, for convenience of explanation, the partitioned space is sequentially provided in a direction from the supply reel 420 to the recovery reel 440 in the first deposition space 262, the second deposition space 263, and the third deposition space ( 264), a fourth deposition space 265 , a fifth deposition space 266 , and a post-heat treatment space 268 will be described.

In addition, the lower chamber 260 ^{is maintained in a high vacuum state of 10 -4} Torr or less by exhaust pumping, and the first to fifth deposition spaces 262 to 266 and the lower post-heat treatment space 268 contain deposition materials, respectively. A deposition method according to the characteristics and an apparatus configuration for this are added.

Meanwhile, when the lower chamber partitioning step is completed as described above, the upper chamber partitioning step of partitioning the inner space of the upper chamber to correspond to the partitioned space of the lower chamber is performed.

In the upper chamber partitioning step, the upper partitioning member 600 is installed to correspond to the installation position of the lower partitioning member 800 to divide the inner space into six spaces, respectively, a first reaction space 222 and a second reaction space. 223 , a third reaction space 224 , a fourth reaction space 225 , a fifth reaction space 226 , and an upper post-heat treatment space 228 .

On the other hand, although the vacuum state is maintained by the exhaust pumping in the upper chamber 220 divided as described above, as described above, as oxygen and/or reaction gas are supplied through the oxygen supply unit 500, a relatively low vacuum state is maintained as

The oxygen supply unit 500 is located in the third reaction space 224 and the upper post-heat treatment space 228 where the superconducting layer is located, and for convenience of explanation, a first oxygen supply unit 520 and a second oxygen supply unit ( 540).

When the upper chamber partitioning step is completed as described above, a deposition step in which the deposition material is sequentially deposited by transferring the substrate 100 while rotating the guide drum 400 positioned between the plurality of deposition and reaction spaces is performed.

Hereinafter, a process for manufacturing a high-temperature superconducting wire of the present invention will be described with reference to specific embodiments of the present invention.

In this embodiment, the guide drum 400 has a diameter of 50 cm and a length of 72 cm, and accommodates a wire rod having a length of 100 m.

The guide drum 400 is rotationally controlled at 100 rpm, and all deposition processes are equally applied.

Meanwhile, in each deposition space, deposition materials are disposed as shown in the table below to control operating conditions.

division	deposition material	vapor deposition	deposition temperature	degree of vacuum	deposition rate
first deposition space	Y 2 O 3	electron beam deposition		room temperature	10 -4 Torr or less	several nm/sec
2nd deposition space	MgO	electron beam deposition		room temperature	10 -4 Torr or less	several nm/sec
3rd deposition space	Ag	thermal evaporation	600℃	10 -4 Torr or less	tens/sec
4th deposition space	SmBCO	Simultaneous thermal evaporation	800℃	5-20mTorr	several nm/sec
5th deposition space	Ag	thermal evaporation	500~700℃	10 -4 Torr or less	several nm/sec

In detail, in the first deposition space 262 , yttrium oxide (Y ₂ O ₃ ) is accommodated as a deposition material, and when the substrate 100 is supplied while the guide drum 400 is rotated, the yttrium oxide is formed into a thin film by electron beam deposition at room temperature. is deposited with Then, the yttrium oxide deposited in the form of a thin film is moved to the first reaction space 222 by rotation, and the yttrium oxide layer is formed by diffusion and crystal growth. The substrate 100 on which the yttrium oxide layer is deposited as described above is transferred to the second deposition space 263 by rotation of the guide drum 400, and magnesium oxide ( MgO) is deposited in the form of a thin film. Then, magnesium oxide (MgO) deposited in the form of a thin film is transferred to the second reaction space 223 by rotation to form a magnesium oxide layer while diffusion and crystal growth. The substrate on which the magnesium oxide layer is formed as described above is again guided It is transferred to the third deposition space 264 by the rotation of the drum 400 , and silver (Ag), which is a crystal orientation improving material for improving crystal orientation, is deposited in the form of a thin film in the third deposition space 264 . As described above, the silver (Ag) deposited in the form of a thin film is transferred to the third reaction space 224 by rotation to improve crystal orientation while diffusion and crystal growth to form a single-crystal level silver (Ag) thin film. That is, silver (Ag) accommodated in the third deposition space 264 is an example of a material for improving crystal orientation, Fe, Fe-based alloy, Fe-based compound, Ni, Ni-based alloy, Ni-based compound, It may be selected from Ag or Cu, and the crystal orientation improvement mechanism for selecting such a material will be described in detail with the accompanying drawings below.

As described above, the substrate on which the silver (Ag) thin film of the single crystal level is formed is transferred to the fourth deposition space 265 by the rotation of the guide drum 400 again, and in the fourth deposition space 265 , Sm, Ba, Cu SmBCO is deposited in the form of a thin film by co-evaporation. At this time, the SmBCO is transferred to the fourth reaction space 225 as the silver (Ag) thin film is formed at a single crystal level, and grows epitaxially according to the crystal orientation of the single crystal level when the crystal is grown to form a single crystal level superconducting thin film. .

As described above, the substrate on which the superconducting thin film of the single crystal level is formed is transferred to the fifth deposition space 266 by the rotation of the guide drum 400 again, and silver (Ag) is formed in the form of a thin film in the fifth deposition space 266 . It is laminated and formed as a silver (Ag) protective layer while passing through the fifth reaction space 226 .

After the deposition of the silver (Ag) protective layer on the substrate is completed as described above, the substrate is transferred to the recovery roll 440 in the lower post heat treatment space 268 and the upper post heat treatment space 228 by the rotation of the guide drum 400 . After the winding is completed, the oxygen composition ratio of the superconducting layer, which is insufficient during deposition, is adjusted to the optimum composition ratio by supplying several hundred Torr of oxygen while heating to 450°C.

On the other hand, Figure 8 is a view for showing the single crystal formation mechanism of the present invention is shown.

Referring to the drawings, the substrate formed of the polycrystalline first material may have a shape in which the orientation axis direction of each crystal grain constituting the layer is randomly formed (refer to (a) of FIG. 8).

A thin film is formed by depositing a polycrystal orientation improving material on the upper side of the polycrystal substrate as described above, but during the deposition, crystal nuclei larger than the grain size of the substrate crystal grains are generated while crystal growth of the crystal orientation improving material A thin film is deposited.

That is, when the crystal orientation improving material is deposited, crystal nuclei are instantaneously generated and grown on the substrate while being deposited, and are generated larger than the grain size of the crystal at the grain boundary of the substrate, at this time the crystal grains of the thin film are formed. When the direction of the alignment axis coincides with the average direction of the alignment axis of the crystal grains of the substrate, the energy is lowest, so that deposition can be performed parallel to the alignment direction of the average alignment axis of the substrate (refer to FIG. 8(b) ).

To this end, the grain size of the crystal orientation improving material deposited on the upper side of the substrate is at least twice the size of the substrate grain size, and more preferably, when it is 5 to 6 times or more, the average direction of the orientation axis of the substrate grains and the crystal grains of the thin film The orientation direction can be almost coincident. Thereafter, as the deposition of the crystal orientation improving material continues, the crystal nuclei grow and the thin film deposition is completed, the crystal grain orientation of the thin film shows single crystallinity in which the half-width of the crystal orientation difference angle at the grain boundary satisfies within 3°. (see Fig. 8(c))

More specifically, FIG. 9 is a view showing a FeCo thin film as a crystal orientation improving material according to a preferred embodiment of the present invention.

9 (a) is an SEM photograph of the surface of the FeCo alloy thin film. Referring to this, the FeCo thin film has a rectangular FeCo crystal shape, and the alignment axis is straight and uniformly aligned, which is oriented at the level of a single crystal. It means that the crystal nuclei are generated in a state where the crystals are grown and a thin film is formed as the crystals grow epitaxially.

That is, in spite of the formation of a polycrystalline FeCo alloy thin film on a polycrystalline substrate, the average orientation axis direction and alignment direction of the substrate crystal grains coincide with each other, and as the FeCo thin film is deposited parallel to the average orientation axis alignment direction of the substrate, the single crystal A FeCo thin film is formed.

In addition, (b) of FIG. 9 shows the cross section of the FeCo alloy thin film as a TEM photograph. Referring to this, it is clearly shown that crystal growth occurs epitaxially from the interface between the LMO layer and the FeCo alloy thin film. Here, the LMO layer is a polycrystalline buffer layer for improving the bonding strength of the FeCo alloy thin film, which is a crystal orientation improving material layer of the substrate. Such a structure will be described in more detail with reference to the accompanying drawings below.

And, (c) of FIG. 9 is a SEM photograph showing the surface at a thickness of 400 nm or less of a FeCo alloy thin film deposited through thermal evaporation at a temperature of 600° C. or higher, wherein the FeCo crystals of the FeCo alloy thin film have a square shape. appear to be sorted.

In addition, in the case of (d) of FIG. 9, the surface at a thickness of 400 nm or more of the FeCo alloy thin film formed by deposition through thermal evaporation at a temperature of 400 to 600 ° C is shown as an SEM photograph. indicates that it has a surface.

Therefore, in the present invention, in the thin film for improving crystal orientation, as described above, when the crystal orientation improving material layer is deposited, the crystal nuclei are generated and the crystals grow epitaxially, and when the crystal nuclei are generated, the energy is the lowest in FeCo Since the crystal orientation of the thin film is controlled, crystal orientation of a single crystal level is exhibited almost simultaneously with the deposition of the crystal orientation improving material.

Preferably, the crystal orientation improving material layer of the present invention is deposited such that the crystal orientation is parallel to the average direction of the orientation axis of the substrate crystal grains within several tens of nm from the interface with the substrate, and as the crystals are epitaxially grown and deposited as a thin film, hundreds of It may be formed as a single crystalline thin film ranging from nm to several μm. More preferably, it exhibits single crystallinity satisfying the relation A within 40 nm from the interface with the substrate formed under the crystal orientation improving material layer of the present invention.

[Relational A]

0°< FWHM ₂ ≤ 3°

(However, FWHM ₂ is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)

In addition, in the present invention, the crystal orientation improving material of the polycrystal may be Fe, an Fe alloy, or a Fe-based compound. At this time, as the thin film formed of the Fe-based crystal orientation improving material, that is, the crystal orientation improving material layer, has a body-centered cubic (bcc) structure, angles parallel to the average direction of the orientation axes of the substrate crystal grains The crystal nuclei located at the center of the crystal may be deposited while oriented.

In addition, Fe is the second most common metal in the Earth's crust after aluminum and has the highest specific gravity among elements constituting the Earth. Therefore, the Fe-based single crystalline thin film can be applied to the present invention because it can increase economic feasibility in terms of cost as well as have excellent crystal orientation, and can exhibit excellent crystal orientation regardless of the type of polycrystalline substrate.

In this case, preferably, the Fe-based thin film may be a thin film formed of an alloy of Fe, Co and/or Ni.

More preferably, it may be Fe _x Co _1-x (provided that 0≤x≤0.5) or FeNi ₃ .

In addition, the crystal orientation improving material forming the thin film may be any one selected from Fe, Fe-based alloy, Fe-based compound, Ni, Ni-based alloy, Ni-based compound, Ag, or Cu.

_{10 is a graph showing the analysis of 2-theta according to the composition ratio of the thin film formed of the Fe x} Co _1-x alloy according to an embodiment of the present invention, and related to the deposition site of iron and cobalt for measuring the crystal orientation of the FeCo thin film. , means that the closer to #1, the higher the composition ratio of iron, and the closer to #7, the higher the composition ratio of cobalt. Referring to this, even if the composition ratios of iron and cobalt are different, it appears that the degree of alignment in the plane direction of the crystals is maintained.

_{From these results, it is implied that the Fe x} Co _1-x thin film can be commercialized as a single crystalline thin film, as it is not sensitive to the composition ratio between iron and cobalt and maintains the crystal orientation well without a significant difference in the crystal orientation according to the change in the composition ratio. do.

Meanwhile, FIG. 11 is a diagram showing the alignment of crystals in the plane direction by analyzing Phi Scan by applying MgO and LMO as a polycrystalline buffer layer according to an embodiment of the present invention. (However, Phi Scan is a plane view. When viewed at a 360° angle, the cube texture should show 4 peaks, and the sharper each peak, the better the alignment).

Referring to this, the average half width of the polycrystalline buffer layer made of MgO grown in the forward direction through the peaks at 0°, 90°, 180°, and 270° is 6.8°, and at 45°, 135°, 225°, and 315° It was found that the average half width of the thin film made of the crystal orientation improving material of the FeCo alloy grown in the 45° direction was 2.6° ((a) of FIG. 11), 0°, 90°, 180°, The average half-width of the substrate containing LMO grown in the forward direction through the peaks at 270° is 6.8°, and the peaks at 45°, 135°, 225°, and 315° of the FeCo alloy grown in the 45° direction. It was found that the average half width of the thin film made of the crystal orientation improving material was 2.9° (FIG. 11(b)).

That is, the FeCo thin film deposited regardless of the type of the polycrystalline buffer layer exhibited a full width at half maximum within 3°, so it can be confirmed that the same monocrystalline orientation is exhibited even if the type of the polycrystalline buffer layer is different.

12 is a view showing the crystal orientation ability according to the half width of the crystal orientation difference angle of the crystal grains at the grain boundary of the polycrystalline buffer layer according to an embodiment of the present invention. MgO is applied as the polycrystalline buffer layer, and the crystal orientation improving material This shows the crystal orientation ability by analyzing the Phi Scan by applying the same FeCo to the polycrystalline buffer layer, but changing only the half width of MgO in the polycrystalline buffer layer.

With reference to this, FIG. 12a shows that the average half-width of the substrate including MgO grown in the forward direction through peaks at 0°, 90°, 180°, and 270° is 6.8°, 45°, 135°, 225°, 315 The average of the half width of the thin film made of the crystal orientation improving material of the FeCo alloy grown in the 45° direction through the peak at ° is 2.8°, and FIG. 12b shows the peaks at 0°, 90°, 180°, and 270°. The average half-width of the substrate containing MgO grown in the forward direction through It was found that the average half width of the formed thin film was 2.6°.

From these results, even if the crystal orientation difference angle of the average orientation axis of the substrate on which the polycrystalline buffer layer is formed is biased to 6.8° or 13.53°, the overall orientation axis average direction of the grains of the substrate is in one direction, so even if the crystal orientation ability of MgO, the polycrystalline buffer layer, is poor It can be seen that the FeCo thin film is oriented to a single crystal level.

Therefore, in the present invention, the crystal orientation improving material of the polycrystal on the polycrystalline buffer layer exhibits single crystallinity as the crystal orientation is oriented. It is characterized in that the crystal orientation of the polycrystalline buffer layer and the crystal orientation improving material layer _{satisfies 0°< FWHM 2} ≤ 3° while satisfying the following [Relational Expression B].

[Relation B]

5°< FWHM ₁ - FWHM ₂ ≤ 20°

(However, FWHM ₁ and FWHM ₂ are the full width at half maximum of the distribution curve of the misorientation angle at the grain boundary of the substrate and the thin film, respectively.)

That is, the size of the crystal grains formed while the crystal orientation improving material forming the single-crystal thin film is deposited is at least twice the size of the crystal grains of the substrate, the crystal nuclei are generated, and the orientation is made as the crystal grows, There is a significant difference between the full width at half maximum at the grain boundary of the substrate and the half width of the thin film exhibiting single crystallinity.

In particular, as the deposition rate increases, the crystal nuclei grow rapidly and a thin film can be formed at the level of a single crystal, and the IBAD and RABiTS metal substrates applied to superconductors have an average crystal orientation difference of 6°, and at the grain boundaries of commonly used substrates. Since the half width of the crystal orientation difference angle is about 20° at most, as described above, the crystal orientation of the substrate and the thin film satisfies the relation B, while the crystal orientation of the thin film satisfies 0°< FWHM ₂ ≤ 3°. will be.

On the other hand, in the step of forming the thin film according to the present invention, crystal nuclei are generated when the crystal orientation improving material of polycrystals is deposited on the upper portion of the substrate, and the crystals grow epitaxially to form a thin film, so that the crystal nuclei are generated. Since the crystal orientation of the thin film is controlled with the lowest energy when the material is deposited, the crystal orientation improving material is deposited and exhibits a single crystal level of crystal orientation, thereby satisfying the aforementioned Relations A and B.

At this time, as the deposition method, chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), spin-on-glass (Spin-On-Glass) , SOG), plating and other various methods can be used. Preferably, in the step of forming the thin film, a CVD method using heat or plasma, a PVD method using thermal evaporation, electron beam or sputtering, which forms a thin film by vacuum deposition to control the structure of the thin film and improve crystal orientation is available.

13 is a view showing the crystal orientation ability according to the deposition rate of the crystal orientation improving material in the step of forming a thin film by depositing the crystal orientation improving material by thermal evaporation according to an embodiment of the present invention.

That is, the Phi Scan analysis result of the crystal orientation ability according to the deposition rate of the crystal orientation improving material of the present invention shown in FIGS. is shown as However, the average of the half-width of the substrate including MgO grown in the forward direction through the peaks at 0°, 90°, 180°, and 270° is 6.8°.

Referring to this, FIG. 9a shows that the average half width of the thin film made of the crystal orientation improving material of the FeCo alloy grown in the 45° direction through the peaks at 45°, 135°, 225°, and 315° is 1.5°. and the deposition rate was 40 Å/sec. In addition, FIG. 13b shows that the average half-width of the thin film made of the crystal orientation improving material of the FeCo alloy grown in the 45° direction through the peaks at 45°, 135°, 225°, and 315° is 3.5°. In this case, the deposition rate is a deposition rate that starts from 0 at the deposition starting point and increases by 40 Å/sec. In addition, (c) of FIG. 13 shows that the average half-width of the thin film made of the crystal orientation improving material _{of FeNi 3} grown in the 45° direction through peaks at 45°, 135°, 225°, and 315° is 1.5°. , and the deposition rate at this time was 40 Å/sec.

From the results of (a) to (c) of FIG. 13, when the deposition rate is high, the generation of crystal nuclei and the growth of the crystal are fast, so that the size of the crystal grains is increased to increase the crystal orientation, and when the deposition rate is small, the generation of crystal nuclei And it can be confirmed that as the crystal growth is made relatively slowly, the size of the crystal grains is small and the crystal orientation is lowered. Therefore, the higher the deposition rate, the higher the crystal orientation. In addition, as a crystal orientation improving material, Fe-based material has a body-centered cubic structure, so that crystal orientation is improved when deposited at a high deposition rate while crystal nuclei located at the center of each crystal are oriented parallel to the average direction of the orientation axes of the crystal grains of the substrate. rises

14 is a view showing the crystal orientation ability according to the deposition temperature in the step of forming a film by depositing the crystal orientation improving material by the thermal evaporation method according to an embodiment of the present invention, the crystal orientation capability of the FeCo thin film according to the deposition temperature shows the results confirmed by the FeCo (002) peak. That is, in (a) to (h) of Figure 14, the crystal orientation improvement material when the substrate temperature is 150 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, respectively, FeCo alloy The XRD result of the thin film is shown. Referring to this, it was shown that FeCo is amorphous at a substrate temperature of 150°C and crystallized from 200°C.

Therefore, preferably, in the step of forming a thin film with the Fe-based crystal orientation improving material, deposition may be performed at at least 200° C., more preferably at 500 to 600° C. Compared to the general metal thin film formation that is required to be deposited at a high temperature of 700° C. or higher, it can be confirmed that the crystal orientation ability is very excellent, especially when the thin film is formed with an Fe-based crystal orientation improving material.

As described above, according to the present invention, the step of forming a thin film by depositing a polycrystal orientation improving material on the substrate can have a high crystal orientation of a single crystal level by controlling the deposition temperature and the deposition rate.

15 is a view showing experimental results on the thickness showing the crystal orientation of a single crystal level, and shows the crystal orientation timing during deposition according to the thickness of the FeCo alloy among the Fe alloys as the crystal orientation improving material. That is, when the FeCo thin film is deposited on the substrate by varying the lengths of (a) 40 nm, (b) 80 nm, and (c) 120 nm, the distribution of the Fe(110) crystal plane direction is spontaneously aligned within 0.5° at the same time as the deposition, so that the single crystal level indicates the crystal orientation of

Therefore, according to the single crystal formation mechanism of the present invention, the thin film formed of the crystal orientation improving material layer is deposited so that the crystal orientation is parallel to the average direction of the orientation axis of the crystal grains of the substrate within several tens of nm from the interface with the substrate on which the polycrystalline buffer layer is formed. More preferably, the crystal orientation improving material layer exhibits single crystallinity satisfying the above-described relational expression A within 40 nm from the interface with the substrate formed under the thin film.

The high-temperature superconducting wire according to the present invention can manufacture a high-temperature superconducting wire in which a single-crystal level superconducting layer is formed using a polycrystalline substrate.

Therefore, it can be applied to power production, power system, and energy consuming industries, as well as high temperature low magnetic field fields and low temperature high magnetic field fields, and based on this, it can be applied to more diverse product fields.

In addition, while the global superconducting market is estimated to exceed 113 billion dollars in 2050, the super-grid for sharing power resources through linking multi-country power grids and national policy trends for nurturing superconducting technology Since the size and application range of the superconducting market is expected to be further expanded, the industrial applicability of the present invention is expected to be higher.

Claims (6)

1. vacuum chamber;

   a plurality of deposition spaces partitioned by partition members for each deposition material provided inside the vacuum chamber;

   a guide drum having a length passing through all of the plurality of deposition spaces inside the vacuum chamber, and having a guide groove formed on an outer surface thereof to guide the movement of the substrate;

   a supply reel provided on one side of the guide drum inside the vacuum chamber to supply a substrate along the guide groove;

   a recovery reel provided on the other side of the guide drum inside the vacuum chamber to recover the substrates that have passed through the plurality of deposition spaces; and

   The partition member constitutes a vacuum chamber, a lower partition member for preventing the inflow of each deposition material into another space in the lower chamber providing an evaporation space of the deposition material, and a reaction space of the material deposited on the substrate constituting the vacuum chamber It is configured to include; an upper partition member for partitioning the upper chamber to correspond to the partition position of the lower chamber,

   Each surface of the upper partition member and the lower partition member is formed to correspond to the shape of the outer surface of the drum.
2. The method of claim 1,

   The deposition material accommodated in the deposition space includes a material having a crystal orientation of a single crystal level by satisfying [Relational Equation A].

   [Relational A]

   0°< FWHM2 ≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)
3. The method of claim 1,

   The lower and upper chambers are provided with lower fixing means and upper fixing means arranged at equal intervals along the longitudinal direction of the guide drum, respectively, and the lower and upper partition members are fixed to the lower part according to the required space. A high-temperature superconducting wire manufacturing apparatus, characterized in that it is fitted to the means and the upper fixing means while changing positions.
4. A guide drum preparation step including a guide drum for transferring a substrate in a reel-to-reel manner in a vacuum chamber;

   a lower chamber partitioning step of disposing a deposition material deposited on a guide drum inside the vacuum chamber and partitioning each deposition material arrangement space using a lower partition member;

   an upper chamber partitioning step of partitioning an inner space of the upper chamber using an upper partitioning member to correspond to the lower chamber partitioning step;

   A method of manufacturing a high-temperature superconducting wire, comprising: a deposition step of sequentially depositing deposition materials while rotating a guide drum in a vacuum chamber having an internal space partitioned thereon.
5. 5. The method of claim 4,

   In the lower chamber partitioning step, a high temperature superconducting wire manufacturing method, characterized in that when the deposition material is disposed, a material having a single crystal level crystal orientation is disposed in front of the arrangement space of the material forming the superconducting layer by satisfying [Relational Equation A].

   [Relational A]

   0°< FWHM2 ≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)
6. 5. The method of claim 4, wherein the depositing step

   A first deposition process of depositing _{yttrium oxide (Y 2} O ₃ ) on a substrate in a partitioned first space;

   A second deposition process of depositing magnesium oxide (MgO) in an IBAD method on the substrate on which the yttrium oxide (Y ₂ O _{3 ) is deposited in the partitioned second space;}

   A third deposition process in which a single crystal level orientation deposition is performed by depositing a material having a single crystal level crystal orientation by satisfying [Relational Equation A] on a substrate on which a magnesium oxide (MgO) layer is deposited in the partitioned third space;

   A fourth deposition process of depositing a superconducting layer using a simultaneous thermal evaporation method on the upper side of the crystal orientation improving material layer orientation-deposited at a single crystal level in the divided fourth space;

   a fifth deposition process of forming a protective layer by depositing silver (Ag) on the upper side of the superconducting layer in the divided fifth space; and

   A sixth process of controlling the oxygen composition ratio of the superconducting layer by supplying oxygen into the sixth space after winding all the substrates completed up to the fifth deposition process on a recovery reel in the divided sixth space; characterized in that it comprises a A method for manufacturing a high-temperature superconducting wire.

   [Relational A]

   0°< FWHM2 ≤ 3° (However, FWHM2 is the full width at half maximum of the misorientation angle distribution curve at the grain boundary of the thin film.)

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