KR101261802B1 - Apparatus for deposition - Google Patents

Abstract

The present invention is directed to a deposition chamber, a tubular support disposed in the deposition chamber, a first target for supplying a first material disposed in the deposition chamber and to be deposited onto the surface of the tubular support, and disposed in the deposition chamber. A second target for supplying a second material to be deposited onto the tubular support surface, a first power supply for supplying a voltage to the first target, and a second power supply for supplying a voltage to the second target And a gas supply means for supplying a gas for plasma formation in the deposition chamber, wherein the tubular support is rotated in conjunction with the rotation of the holder on which the tubular support is mounted. According to the present invention, ceramic and metal can be simultaneously deposited for complexing a conductive oxide and a metal, and ion bombardment of two targets is controlled by independently controlling power supplied to the first target and the second target. Since the strength can be adjusted, it is possible to control the film quality deposited on the surface of the tubular matrix, and since the tubular support rotates and revolves, particles sputtered from the first target and the second target can be deposited evenly without being biased.

Description

[0001] Apparatus for deposition [0002]

The present invention relates to a deposition apparatus, and more particularly, to simultaneously deposit a ceramic and a metal for complexing a conductive oxide and a metal, and independently controlling the power supplied to the first target and the second target to target two targets. It is possible to control the intensity of ion bombardment on the surface, thereby controlling the film quality deposited on the surface of the tubular matrix, and the particles sputtered from the first target and the second target are biased because the tubular support rotates and revolves. The present invention relates to a deposition apparatus that can be deposited evenly.

Hydrogen energy is in the spotlight as an alternative energy source that can solve the problem of depletion and pollution of fossil fuels such as oil and coal. Techniques for producing hydrogen molecules include various methods such as electrolysis of water, biochemical reaction by microorganisms, filtration of natural hydrogen molecules, and production using high temperature heat.

However, most of the methods are difficult to secure hydrogen as an energy source due to cost and the like, and thus, active researches have been conducted to separate high-purity hydrogen molecules by filtration from low-purity or waste hydrogen-containing gases. .

As a method for separating hydrogen mixed with nitrogen, oxygen, carbon dioxide, carbon monoxide, etc., there have been attempts to separate using a membrane having a nanometer (pores) sized pores. However, to date, there is a difficulty in producing a hydrogen separation membrane having a uniform pore structure and has not reached the stage of obtaining high purity hydrogen.

As a method for obtaining high purity hydrogen, a technique for separating and purifying pure hydrogen only at a high temperature has been studied. Representative hydrogen separation membrane material is a perovskite structure having a composition of ABO ₃ . The most studied compositions are SrCeO ₃ and BaCeO ₃ , which have excellent durability but low separation characteristics. According to a recent study (Korean Patent Registration No. 10-0691645), BaCe _x YM _1-x O ₃ and LaSr _x M _1-x O ₃ (M = La, Y, Yb, Ga, Gd) to improve hydrogen separation characteristics , In, Ge), and the like are being studied. Metal nanoparticles such as Ni, Pt, Rh, and Pd are added thereto to prepare ceramic-metal nanocomposites to further improve hydrogen separation characteristics.

However, the improvement of the hydrogen separation characteristics of the material does not completely solve the method for producing high purity hydrogen. As studied in Korean Patent Registration No. 10-0691645, an oxide that is a raw material is usually mixed in a required ratio, and then sintered into a plate shape at a high temperature of 1400 ° C. or above, and the separator is polished into a flat plate.

Hydrogen separation characteristics tend to increase rapidly as the thickness becomes thinner. However, the thickness of the hydrogen separation membrane body is limited to a thickness that does not break during the polishing process. In general, the limit of grinding is about 0.1 mm level, and if you want to obtain a lower thickness than this problem is frequently caused by breakage. Therefore, although the ion conductivity of the separator material is improved by the conventional technology, the use of the separator itself by grinding the separator in a flat plate has many limitations in order to achieve the purpose of hydrogen separation.

On the other hand, the hydrogen separation method using a plate-type hydrogen separation membrane is a gas containing hydrogen in one direction based on the plate-type hydrogen separation membrane by installing a hydrogen separation module inside the chamber blocked from the outside (for example, carbon dioxide and hydrogen gas Gas) and the hydrogen passing through the hydrogen separation membrane is collected by collecting hydrogen separation in the other direction based on the plate-type hydrogen separation membrane.

However, the above-described hydrogen separation efficiency of the plate-type hydrogen separation membrane is not high, and if the mixed gas containing hydrogen is continuously injected, the pressure in the chamber may be increased, and there may be a risk of explosion. In addition, there are difficulties in discharging gas such as carbon dioxide remaining after hydrogen separation, and there are many difficulties in capturing hydrogen passing through a plate-type hydrogen separation membrane, and thus a hydrogen separation device using a plate-type hydrogen separation membrane. There has been a serious problem in durability.

In consideration of this, the patent application No. 10-2008-0030567 filed by the applicant has proposed a tubular hydrogen separation membrane body. The hydrogen separation membrane body includes a tubular support and a hydrogen separation membrane formed by being deposited or coated on the tubular support. In general, it is difficult to deposit a hydrogen separation membrane having a uniform thickness on the tubular support, thus requiring a new deposition apparatus. It is becoming.

The problem to be solved by the present invention is to deposit a ceramic and a metal at the same time for the complex of the conductive oxide and metal, and to control the power supplied to the first target and the second target independently to ion bombardment (ion) The intensity of the bombardment can be controlled to control the film quality deposited on the surface of the tubular matrix, and the sputtered particles from the first and second targets can be deposited evenly without being biased because the tubular support rotates and revolves. The present invention provides a deposition apparatus.

The present invention is directed to a deposition chamber, a tubular support disposed in the deposition chamber, a first target for supplying a first material disposed in the deposition chamber and to be deposited onto the surface of the tubular support, and disposed in the deposition chamber. A second target for supplying a second material to be deposited onto the tubular support surface, a first power supply for supplying a voltage to the first target, and a second power supply for supplying a voltage to the second target And a gas supply means for supplying a gas for plasma formation in the deposition chamber, wherein the tubular support is rotated in conjunction with the rotation of the holder on which the tubular support is mounted.

The tubular support may be provided to revolve at regular intervals in association with rotation of a holder support for supporting the holder.

The holder support is rotated by being connected to the rotary drive means, the tubular support can be revolved at a speed of 1 ~ 100 sec / cycle in conjunction with the rotation of the holder support.

The first target and the second target are arranged at an angle θ in the range of 90 ° <θ <180 ° relative to the tubular support so that the flux of the material to be deposited reaches the tubular support evenly. The tubular support is preferably located in a region where the region where the flux of particles sputtered from the first target is distributed and the region where the flux of particles sputtered from the second target are distributed.

The deposition apparatus may further include a third target disposed in the deposition chamber and for supplying a third material to be deposited onto the tubular support surface.

The deposition apparatus may further include a shutter for shielding the third target, and the shutter is provided to be opened and closed by a driving means.

The deposition apparatus may further include a vacuum pump for controlling the pressure in the deposition chamber.

The deposition apparatus may further include a first shutter for shielding the first target and a second shutter for shielding the second target, wherein the first shutter and the second shutter are respectively driven by a driving means. Opening and closing, the first shutter and the second shutter is provided to be opened and closed independently of each other.

The deposition apparatus may further include heating means for adjusting the temperature of the tubular support, and when the material is deposited on the surface of the tubular support, the temperature of the tubular support is 300 to 600 ° C. using the heating means. It is desirable to keep the range constant.

The first target is mounted with a metal or metal alloy material, the second target is mounted with a material of ceramic material, the first target is applied with a DC voltage through the first power supply, the second target A pulse voltage may be applied through the second power supply.

The holder is connected to the rotation drive means is rotated, the tubular support can be rotated at a speed of 1 ~ 100 sec / cycle in conjunction with the rotation of the holder.

The conductive oxide constituting the hydrogen separation membrane has a very low electronic conductivity compared to the ionic conductivity and requires complexation with a metal. According to the deposition apparatus of the present invention, a ceramic and a metal can be deposited simultaneously.

In addition, according to the present invention, since the intensity of ion bombardment for the two targets can be adjusted by independently controlling the power supplied to the first target and the second target, the film quality deposited on the surface of the tubular matrix is controlled. It is possible to do

In addition, according to the present invention, since the tubular support rotates and revolves, particles sputtered from the first target and the second target can be deposited evenly without being biased.

1 is a perspective view illustrating a tubular hydrogen separation membrane body according to one embodiment.
2 is a perspective view illustrating a tubular hydrogen separation membrane body according to another example.
3 is a perspective view showing a tubular hydrogen separation membrane body according to another example.
4 is a conceptual diagram schematically showing a deposition apparatus for forming a tubular hydrogen separation membrane body according to a preferred embodiment of the present invention.
5 is a view schematically showing the flux of particles emitted from the target of the deposition apparatus.
6 and 7 are views showing the appearance of the deposition apparatus according to an embodiment of the present invention.
8 is a Scanning Electron Microscope (SEM) photograph of the hydrogen separation membrane prepared according to Example 1. FIG.
9 is a scanning electron microscope (SEM) photograph of the hydrogen separation membrane prepared according to Example 2. FIG.
FIG. 10 is a graph showing an X-ray diffraction (XRD) pattern of a hydrogen separation membrane prepared according to Example 1 and a hydrogen separation membrane prepared according to Example 2.
FIG. 11 is a graph showing an XRD pattern of a hydrogen separation membrane prepared according to Example 3 and an XRD pattern of a sample obtained by heat treating the hydrogen separation membrane prepared according to Example 2 at 800 ° C. (1073 K) for 1 hour.
12 is a scanning electron microscope (SEM) photograph showing a cross section of the hydrogen separation membrane prepared according to Example 3.
FIG. 13A shows a cross section and FIGS. 13B to 13D are photographs showing element mapping for FIG. 12.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen. Wherein like reference numerals refer to like elements throughout.

Tubular hydrogen separation membrane body is to improve the overall hydrogen separation characteristics by coating the porous tubular support in a thin thickness as possible hydrogen separation membrane material having a hydrogen ion conductivity. The tubular hydrogen separation membrane body is composed of a portion having a hydrogen ion conductivity responsible for hydrogen separation and a tubular support supporting the same. The hydrogen separation membrane material and the tubular support may have various forms for improving hydrogen separation characteristics and various configurations of the system including the membrane body. Hereinafter, nano size means a nanometer (nm) size, it is used to mean a size in the range of 1 to 1000 nm. In addition, hereinafter, the inner side means the direction toward the tube center of the tubular support, the outer side means the direction toward the outside from the tube center of the tubular support.

1 is a perspective view showing a tubular hydrogen separation membrane body according to an embodiment of the present invention.

Referring to FIG. 1, the hydrogen separation membrane body has a tubular support 110 formed therein and provides a porous structure for providing a passage through which hydrogen gas is discharged, and a fine nano size formed on the tubular support 110. The porous coating membrane 120 having pores of the hydrogen separation membrane 130 formed on the outer side of the porous coating membrane 120 and having hydrogen ion conductivity to separate hydrogen from a mixed gas containing hydrogen and discharge it to the tubular support 110. ). The tube 112 inside the tubular support 110 serves as a passage through which hydrogen separated by the hydrogen separation membrane 130 is discharged from the external mixed gas, and the diameter of the tube 112 is the amount of hydrogen gas separated and discharged. It is determined in consideration of, and is preferably about 0.5 to 10 cm. The size of the tubular support 110 may vary depending on needs, but the pores should be well developed to facilitate the flow of hydrogen gas into the tubular support 110. The tubular support 110 is formed with a number of pores of 0.1 to 100㎛ size. The tubular support 110 may be made of a material such as SiC, Al ₂ O ₃ , ZrO ₂ , AlTiO ₃ , which is a ceramic material that does not occur deformation at a temperature of 300 to 900 ° C. at which the hydrogen separation membrane body is used, and the hydrogen separation membrane may be BaCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0 ≦ x <1, SrCe _x YM _1-x O ₃ where , M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, where LaSr _x M _1-x O ₃ , where M is La, Y, Yb, Ga , Gd, In or Ge, x is a real number and 0 ≦ x <1, BaCe _x M _{1- x} O ₃ , where x is a real number and 0 <x <1, M is Y, La, Er , At least one rare earth element selected from Eu and Gd, BaZr _x M _1-x O ₃ , wherein x is a real number, 0 <x <1, and M is 1 selected from Y, La, Er, Eu, and Gd Rare earth elements of the species), BaCe _x Zr _y M _1-xy O ₃ (where x and y are real numbers, 0 <x <1, 0 <y <1, 0 <x + y <1, and M is Y Of, La, Er, Eu, and Gd At least one rare earth element selected from SrCe _x M _1-x O ₃ (where x is a real number, 0 <x <1, and M is at least one rare earth element selected from Y, La, Er, Eu, and Gd) ), SrZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, and M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), and the like. It may be made of a twill material. In addition, the hydrogen separation membrane 130 further includes a conductive metal nanoparticles or conductive ceramic nanoparticles having a size of 10 ~ 200nm for imparting electronic conductivity to hydrogen ion conductivity, the conductive metal nanoparticles are used as the hydrogen membrane body It may be made of metals such as Pt, Ni, Pd, Ag, Mo, Fe, Co, etc., having a melting point higher than 300 to 900 ° C., and the ceramic nanoparticles are made of materials such as CeO ₂ , SnO ₂ , WO ₃ , SiC, and the like. Can be. The porous coating membrane 120 may be made of a material such as SiC, Al ₂ O ₃ , ZrO ₂ , AlTiO ₃ , which is a ceramic material which does not occur deformation at a temperature of 300 to 900 ° C. at which the hydrogen separation membrane body is used.

As another example of the present invention, a tubular hydrogen separation membrane body is shown in FIG. 2. Referring to FIG. 2, the hydrogen separation membrane body has a tubular support 210 and a tubular support 210 having a porosity formed therein and providing a passage through which a mixed gas containing hydrogen is introduced, and formed inside the tubular support 220. And a hydrogen separation membrane 230 having hydrogen ion conductivity to separate hydrogen from the mixed gas containing hydrogen and discharge the hydrogen to the tubular support.

Another example of the present invention shows a tubular hydrogen separation membrane body in FIG. 3. The porous coating membrane 320 formed on the tubular support 310 is the same as that shown in FIG. 1, but the catalyst layer for promoting hydrogen separation and gas reaction before the hydrogen separation membrane 330 having hydrogen ion conductivity is coated ( 340a) may be further introduced. The catalyst layer 340a may be composed of elements such as Pt, Ni, Pd, Ag, Mo, Co, and the like.

The above-described hydrogen separation membrane body is disclosed in detail in Patent Application No. 10-2008-0030567 filed by the present applicant.

Although the tubular hydrogen separation membrane body has been described as including a tubular support and a hydrogen separation membrane, the hydrogen separation membranes 130, 230, and 330 themselves may be formed in a tubular shape.

However, the conductive oxide constituting the hydrogen separation membrane has a very low electronic conductivity compared to the ionic conductivity, and thus requires complexation with a metal. Therefore, a new type of deposition capable of simultaneously depositing ceramic and metal is required. Development of the device is required.

4 is a conceptual diagram schematically showing a deposition apparatus for forming a tubular hydrogen separation membrane body according to a preferred embodiment of the present invention, Figure 5 is a schematic view showing the flux of particles emitted from the target of the deposition apparatus, 6 and 7 are views showing the appearance of the deposition apparatus according to an embodiment of the present invention.

4 to 7, a deposition apparatus for forming a tubular hydrogen separation membrane body forms a plasma around a target made of a material to be deposited on a tubular support disposed in a deposition chamber, and by ion bombardment. A device that allows material to be released from a target to be deposited on a tubular support. When a negative voltage is supplied to the target to accelerate ions from the plasma to the target surface and the accelerated ions collide with the target surface, the material to be deposited from the target is released in the opposite direction to the direction of ion incidence, The material to be transferred is transferred to the tubular support and coated on the surface of the tubular support.

In the vapor deposition apparatus for forming the tubular hydrogen separation membrane body, the tubular support 10 shown in FIGS. 1 to 3 is disposed in the deposition chamber 100. The inner wall of the deposition chamber 100 is coated with an insulator and sealed electrically. The windows 80a and 80b provided to observe the inside may be provided, and an outlet 75 for discharging the gas may be provided.

The tubular support 10 may be provided to be able to rotate and may also be provided to be able to rotate. The tubular support 10 is mounted on the rotatable holder 12 and rotated at a constant speed (eg, 1-100 sec / cycle) for uniform deposition. The holder 12 is connected to the first rotary driving means 16 such as a motor, and is rotatable by driving by the first rotary driving means 16, and the tubular support 10 is rotated according to the rotation of the holder 12. Will also rotate in conjunction. In addition, the holder 12 is connected to the rotatable holder support 14, the holder support 14 is connected to the second rotary drive means 18, such as a motor, to the second rotary drive means 18 The holder support 14 is rotatable by driving, and the holder 12 is revolving at a constant speed (for example, 1 to 100 sec / cycle) according to the rotation of the holder support 14. 10 is also interlocked.

The holder 12 is provided to be controlled by a heating means (not shown) to be controlled at a predetermined temperature (for example, 300 to 600 ° C). The hydrogen separation membrane is deposited and formed by heating the temperature of the holder 100 to a predetermined temperature (for example, 300 to 600 ° C.) using a heating means to deposit the tubular support 10 at a predetermined temperature. It is economical and the process can be simplified because its physical properties are improved and subsequent heat treatment at high temperature is not required.

The vacuum pump 70 is connected to the deposition chamber 100 to maintain the inside of the deposition chamber 100 at a low pressure to make a vacuum state and serves to discharge the gas present in the deposition chamber 100 to the outside. As a result, the pressure in the deposition chamber 100 may be maintained at about 10 ⁻⁷ to 10 ⁻¹ Torr.

Two targets 20 and 30 are arranged at a predetermined angle θ with respect to the tubular support 10, and the angle θ formed by the two targets 20 and 30 is referred to as the tubular support 10. The flux 32 of the material to be deposited is in the range 90 ° <θ <180 ° in order to reach evenly. The tubular support 10 is a region in which a region where the flux 32 of particles sputtered from the first target 20 is distributed and a region where the flux 32 of particles sputtered from the second target 30 are distributed ( Located in A), the tubular support 10 is rotated and revolved in the region A.

The first target 20 includes aluminum (Al), nickel (Ni), titanium (Ti), tantalum (Ta), copper (Cu), molybdenum (Mo), lanthanum (La), yttrium (Y), and europium (Eu). ), A metal or a metal alloy such as gadolinium (Gd), indium (In), gallium (Ga) may be mounted, and the second target 30 may be BaCe _x YM _{1 -x} O ₃ (where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, SrCe _x YM _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <1, LaSr _x M _{1- x} O ₃ , where M is La, Y, Yb, Ga, Gd, In or Ge, x is a real number and 0≤x <C1>, BaCe _x M _{1- x} O ₃ (where x is a real number, 0 <x <1, M is at least one rare earth element selected from Y, La, Er, Eu, and Gd), BaZr _x M _{1 -x} O ₃ (where x is a real number, 0 <x <1, M is one or more rare earth elements selected from Y, La, Er, Eu, and Gd), BaCe _x Zr _y M _1-xy O ₃ (wherein, x, y is a real number, and is 0 <x <1, 0 < y is <1, 0 <x + y <1 And, M is Y, La, Er, Eu and 1 rare-earth element at least one selected from _{Gd), SrCe x M 1-} x O 3 ( where, x is a real number a, 0 <x is <1, M is Y, La , At least one rare earth element selected from Er, Eu and Gd, SrZr _x M _1-x O ₃ (where x is a real number, 0 <x <1, and M is selected from Y, La, Er, Eu, and Gd) At least one rare earth element selected), SiC, ZrO ₂ , Al ₂ O ₂ , CeO ₂ , BaCO ₃ , Y ₂ O ₃ , La ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , ZnO, NiO, CoO, Ceramic material such as CuO may be mounted.

The first target 20 is connected to the first power supply 40 to supply a DC voltage, and the second target 30 is supplied with a pulse voltage that is a voltage at which polarities are alternately connected to the second power supply 50. do. The first power supply 40 and the second power supply 50 are provided to be controlled independently of each other. The DC voltage supplied from the first power supply 40 may be independently supplied to the first target 20, and the pulse voltage supplied from the second power supply 40 may be independently supplied to the second target 30. have. Therefore, since the intensity of ion bombardment for the two targets 20 and 30 can be adjusted by independently controlling the power supplied to the first target 20 and the second target 30, the tubular matrix body ( 10) It is possible to control the film quality deposited on the surface.

The first target 20 is shielded by a first shutter 25a, which is connected to a drive means 92a, such as a motor, via a connecting portion 90a and connected to the first target 95. In the case of depositing the mounted material, it is opened by the driving means 92a for driving opening and closing of the first shutter 25a. The second target 30 is shielded by the second shutter 25b, and the second shutter 25b is connected to the driving means 92b such as a motor through the connecting portion 90b and to the second target 30. In the case of depositing the mounted material, it is opened by the driving means 92b for driving the opening and closing of the second shutter 25b. The first shutter 25a and the second shutter 25b are opened and closed by driving means, respectively, and the first shutter 25a and the second shutter 25b are provided to be opened and closed independently of each other.

In addition, a third target 95 may be further provided, and the third target 95 is used when forming a composite film made of three or more materials on the tubular support 10. The third target 95 is also shielded by a shutter (not shown), and the shutter shielding the third target 95 is connected to a driving means (not shown) such as a motor through the connecting portion 90c, and the third target. In the case of depositing a material mounted at 95, the material is opened by the driving means for driving opening and closing of the shutter. A power supply unit (not shown) may also be connected to the third target 95 to supply a required voltage.

Permanent magnets or electromagnets (not shown) are disposed on the back of the targets 20 and 30 so that a magnetic field can be formed around the targets 20 and 30, and the permanent magnets or electromagnets are made of a single magnet, It may also be arranged. The permanent magnet or electromagnet forms a magnetic field near the target surface having a component parallel to the surface of the target 20, 30. The magnetic field having a component parallel to the surface of the targets 20 and 30 serves to trap electrons in the plasma near the surface of the targets 20 and 30 to generate many collisions near the surface of the targets 20 and 30. .

Gas supply means 60 is a mass flow controller (MFC) connected to the argon (Ar) gas, nitrogen (N ₂ ) gas or a mixed gas of argon (Ar) and nitrogen (N ₂ ) to the connection pipe 65; ) Into the deposition chamber 100 through (not shown). When the argon (Ar) gas, the nitrogen (N ₂ ) gas, or a mixed gas of argon (Ar) and nitrogen (N ₂ ) is introduced into the deposition chamber 100 by the gas supply means 60, the first target 20. ) And the power applied to the second target 30 make argon (Ar) gas, nitrogen (N ₂ ) gas or a mixed gas of argon (Ar) and nitrogen (N ₂ ) into a plasma state, and positively charged ions in the plasma state. The metal or metal alloy particles mounted on the first target 20 and the ceramic material particles mounted on the second target 30 may collide with the first target 20 and the second target 30 with considerable energy. Sputtered from the target 20 and the second target 30.

The sputtered material 25, 35 is incident on the tubular support 10 to be deposited. Since the tubular support 10 rotates and revolves, particles sputtered from the first target 20 and the second target 30 may be evenly deposited without being biased. In the deposition process, DC power is applied to the first target 20 to cause the metal or metal alloy particles to be sputtered from the first target 20, and then a pulse voltage is applied to the second target 30 so that the ceramic material particles become the second target. Sputtering from 30 may result in a sequential deposition in such a way that metal or metal alloy particles are deposited first on the tubular support 10 and ceramic material particles are deposited later, and vice versa. The ceramic material particles are sputtered from the second target 30 by applying a pulse voltage thereto, and then DC power is applied to the first target 20 so that the metal or metal alloy particles are sputtered from the first target 20. Ceramic material particles may be deposited on the support 10 first, and then the deposition may be carried out in such a manner that metal or metal alloy particles are deposited later, and a DC power source is applied to the first target 20. May be applied and a pulse voltage may be applied to the second target 30 to simultaneously deposit ceramic material particles and metal or metal alloy particles on the tubular support 10.

Hereinafter, a method of manufacturing a hydrogen separation membrane body using the vapor deposition apparatus for forming the tubular hydrogen separation membrane body will be described in more detail, and the present invention is not limited to the following examples.

&Lt; Example 1 >

The tubular support 10 made of zirconia (ZrO ₂ ) is disposed in the deposition chamber 100 of the vapor deposition apparatus for forming a tubular hydrogen separation membrane, and the tubular support 10 is rotated at 25 sec / cycle and the revolution is performed. It was not made.

The vacuum chamber 70 connected to the deposition chamber 100 was used to maintain the inside of the deposition chamber 100 at a low pressure of about 10 ⁻¹ Torr to bring it into a vacuum state.

The angle θ formed between the first target 20 and the second target 30 is about 150 ° in order to evenly reach the flux 32 of the material to be deposited into the tubular support 10. The tubular support 10 is a region in which a region where the flux 32 of particles sputtered from the first target 20 is distributed and a region where the flux 32 of particles sputtered from the second target 30 are distributed ( Located in A), the tubular support 10 allowed only rotation in region A.

Nickel (Ni) is mounted on the first target 20, and BaZr _0.85 Y _0.15 O ₃ is mounted on the second target 30, and 0.4V is applied to the first target 20 through the first power supply 40. DC voltage was supplied, and 600W power was applied to the second target 30 through the second power supply 50 to supply the pulse voltage. Independently controlling the power supplied to the first target 20 and the second target 30 to adjust the ion bombardment strength for the two targets (20, 30) to the surface of the tubular matrix (10) The film quality to be deposited was controlled. Permanent magnets are disposed on the rear surfaces of the targets 20 and 30 so that magnetic fields may be formed around the targets 20 and 30.

Argon (Ar) gas is supplied into the deposition chamber 100 through the gas supply means 60, and the argon (Ar) gas is plasma by the power applied to the first target 20 and the second target 30. And the second target 30 made of nickel (Ni) metal particles mounted on the first target 20 because the positively charged ions in the plasma state collide with considerable energy to the first target 20 and the second target 30. BaZr _0.85 Y _0.15 O ₃ particles mounted at were allowed to sputter from the first target 20 and the second target 30.

The sputtered material 25, 35 was incident on the tubular support 10 to allow deposition. As described above, a DC power is applied to the first target 20 and a pulse voltage is applied to the second target 30 so that the nickel (Ni) metal particles and the BaZr _0.85 Y _0.15 O ₃ particles are simultaneously applied to the tubular support 10. The deposition was made, and the tubular support 10 was not rotated but rotated so that the particles sputtered from the first target 20 and the second target 30 were deposited. The heating means was used to allow deposition at room temperature without heating the holder.

The thickness of the material deposited on the tubular support 10 was about 2.7 μm.

<Example 2>

A tubular support 10 made of zirconia (ZrO ₂ ) is disposed in the deposition chamber 100 of the vapor deposition apparatus for forming a tubular hydrogen separation membrane, and the tubular support 10 is rotated at 25 sec / cycle and 35 sec / cycle. The revolution was made.

The vacuum chamber 70 connected to the deposition chamber 100 was used to maintain the inside of the deposition chamber 100 at a low pressure of about 10 ⁻¹ Torr to bring it into a vacuum state.

The angle θ formed between the first target 20 and the second target 30 is about 150 ° in order to evenly reach the flux 32 of the material to be deposited into the tubular support 10. The tubular support 10 is a region in which a region where the flux 32 of particles sputtered from the first target 20 is distributed and a region where the flux 32 of particles sputtered from the second target 30 are distributed ( Located in A), the tubular support 10 was allowed to rotate and revolve in region A.

Nickel (Ni) is mounted on the first target 20, and BaZr _0.85 Y _0.15 O ₃ is mounted on the second target 30, and 0.4V is applied to the first target 20 through the first power supply 40. DC voltage was supplied, and 600W power was applied to the second target 30 through the second power supply 50 to supply the pulse voltage. Independently controlling the power supplied to the first target 20 and the second target 30 to adjust the ion bombardment strength for the two targets (20, 30) to the surface of the tubular matrix (10) The film quality to be deposited was controlled. Permanent magnets are disposed on the rear surfaces of the targets 20 and 30 so that magnetic fields may be formed around the targets 20 and 30.

Argon (Ar) gas is supplied into the deposition chamber 100 through the gas supply means 60, and the argon (Ar) gas is plasma by the power applied to the first target 20 and the second target 30. And the second target 30 made of nickel (Ni) metal particles mounted on the first target 20 because the positively charged ions in the plasma state collide with considerable energy to the first target 20 and the second target 30. BaZr _0.85 Y _0.15 O ₃ particles mounted at were allowed to sputter from the first target 20 and the second target 30.

The sputtered material 25, 35 was incident on the tubular support 10 to allow deposition. As described above, a DC power is applied to the first target 20 and a pulse voltage is applied to the second target 30 so that the nickel (Ni) metal particles and the BaZr _0.85 Y _0.15 O ₃ particles are simultaneously applied to the tubular support 10. The deposition was performed, and the tubular support 10 allowed to rotate and revolve so that the particles sputtered from the first target 20 and the second target 30 were deposited. The heating means was used to allow deposition at room temperature without heating the holder.

The thickness of the material deposited on the tubular support 10 was measured to be about 2 μm.

<Example 3>

A tubular support 10 made of zirconia (ZrO ₂ ) is disposed in the deposition chamber 100 of the vapor deposition apparatus for forming a tubular hydrogen separation membrane, and the tubular support 10 is rotated at 25 sec / cycle and 35 sec / cycle. The revolution was made.

The vacuum chamber 70 connected to the deposition chamber 100 was used to maintain the inside of the deposition chamber 100 at a low pressure of about 10 ⁻¹ Torr to bring it into a vacuum state.

The angle θ formed between the first target 20 and the second target 30 is about 150 ° in order to evenly reach the flux 32 of the material to be deposited into the tubular support 10. The tubular support 10 is a region in which a region where the flux 32 of particles sputtered from the first target 20 is distributed and a region where the flux 32 of particles sputtered from the second target 30 are distributed ( Located in A), the tubular support 10 was allowed to rotate and revolve in region A.

Nickel (Ni) is mounted on the first target 20, and BaZr _0.9 Y _0.1 O ₃ is mounted on the second target 30, and 0.4V is applied to the first target 20 through the first power supply 40. DC voltage was supplied, and 600W power was applied to the second target 30 through the second power supply 50 to supply the pulse voltage. Independently controlling the power supplied to the first target 20 and the second target 30 to adjust the ion bombardment strength for the two targets (20, 30) to the surface of the tubular matrix (10) The film quality to be deposited was controlled. Permanent magnets are disposed on the rear surfaces of the targets 20 and 30 so that magnetic fields may be formed around the targets 20 and 30.

Argon (Ar) gas is supplied into the deposition chamber 100 through the gas supply means 60, and the argon (Ar) gas is plasma by the power applied to the first target 20 and the second target 30. And the second target 30 made of nickel (Ni) metal particles mounted on the first target 20 because the positively charged ions in the plasma state collide with considerable energy to the first target 20 and the second target 30. BaZr _0.85 Y _0.15 O ₃ particles mounted at were allowed to sputter from the first target 20 and the second target 30.

The sputtered material 25, 35 was incident on the tubular support 10 to allow deposition. As described above, a DC power is applied to the first target 20 and a pulse voltage is applied to the second target 30 so that the nickel (Ni) metal particles and the BaZr _0.85 Y _0.15 O ₃ particles are simultaneously applied to the tubular support 10. The deposition was performed, and the tubular support 10 allowed to rotate and revolve so that the particles sputtered from the first target 20 and the second target 30 were deposited. The temperature of the holder 100 was heated to 400 ° C. (673K) using a heating means to maintain the temperature of the tubular support 10 at about 400 ° C., thereby allowing deposition.

The thickness of the material deposited on the tubular support 10 was measured to be about 2 μm.

FIG. 8 is a scanning electron microscope (SEM) photograph of the hydrogen separation membrane prepared in Example 1, and FIG. 9 is a scanning electron microscope (SEM) photograph of the hydrogen separation membrane prepared in Example 2. FIG.

8 and 9, the hydrogen separation membrane deposited while rotating and revolving of the tubular support according to Example 2 is relatively uniform compared to the hydrogen separation membrane deposited while only rotating the tubular support according to Example 1. It can be seen that it is formed densely in thickness.

FIG. 10 is a graph showing an X-ray diffraction (hereinafter referred to as 'XRD') pattern of a hydrogen separation membrane prepared according to Example 1 and a hydrogen separation membrane prepared according to Example 2. FIG. a) shows the XRD of the hydrogen separation membrane prepared in Example 1 and (b) shows the XRD of the hydrogen separation membrane prepared in Example 2.

Referring to FIG. 10, it can be seen that a peak due to the tubular support (substrate), BaZrO ₃ , and nickel (Ni) is shown.

FIG. 11 is a graph showing an XRD pattern of a hydrogen separation membrane prepared according to Example 3 and a sample obtained by heat treating the hydrogen separation membrane prepared according to Example 2 at 800 ° C. (1073 K) for 1 hour. a) shows the XRD of the hydrogen separation membrane prepared in Example 3 and (b) shows the XRD of the sample obtained by heat-treating the hydrogen separation membrane prepared in Example 2 for 1 hour at 800 ℃ (1073K).

Referring to FIG. 11, in the sample heat-treated for 1 hour at 800 ° C. (1073 K), the hydrogen separation membrane prepared according to Example 2 showed peaks due to ZrO ₂ and nickel oxide (NiO). In the hydrogen separation membrane prepared according to Example 3, it can be seen that a peak due to ZrO ₂ and nickel (NiO) appears.

12 is a scanning electron microscope (SEM) photograph showing a cross section of the hydrogen separation membrane prepared according to Example 3, FIG. 13A shows a cross section, and FIGS. 13B to 13D are photographs showing element mapping for FIG. 12.

12 and 13, it can be seen that a hydrogen separation membrane is formed uniformly and densely without defects such as cracks.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, This is possible.

10: tubular support 12: holder
14: holder support 16: first rotation drive means
18: second rotary drive means 20: first target
25a, 25b: shutter
30: second target 32: flux
40: first power supply unit 50: second power supply unit
60: gas supply means 65: connector
70: vacuum pump 92a, 92b: drive means
95: third target

Claims (11)

Deposition chamber;
A tubular support disposed in the deposition chamber;
A first target disposed in the deposition chamber and for supplying a first material to be deposited onto the tubular support surface;
A first shutter for shielding the first target;
First driving means for driving the first shutter;
A second target disposed in the deposition chamber and for supplying a second material to be deposited onto the tubular support surface;
A second shutter for shielding the second target;
Second driving means for driving the second shutter;
A first power supply for supplying a voltage to the first target;
A second power supply unit for supplying a voltage to the second target; And
Gas supply means for supplying a gas for plasma formation in the deposition chamber,
The tubular support is rotated in conjunction with the rotation of the holder in which the tubular support is mounted,
The tubular support is revolved at regular intervals in association with the rotation of the holder support for supporting the holder.
The first target and the second target are arranged at an angle θ in the range of 90 ° <θ <180 ° with respect to the tubular support so that the flux of the material to be deposited reaches the tubular support evenly.
The tubular support is located in an area where an area where flux of particles sputtered from the first target is distributed and an area where flux of particles sputtered from the second target are distributed overlap each other.
Rotation and revolution of the tubular support are performed in a region where a flux of particles sputtered from the first target is distributed and a region where a flux of particles sputtered from the second target is distributed, overlapping.
The first shutter and the second shutter is provided to be opened and closed independently of each other,
DC voltage is applied to the first target through the first power supply unit,
The second target is applied with a pulse voltage which is a voltage whose polarity is alternated through the second power supply,
The first power supply and the second power supply is provided to be controlled independently of each other,
The first target is mounted with a metal or metal alloy material,
And the ceramic material is mounted on the second target.
delete The deposition apparatus of claim 1, wherein the holder support is rotated by being connected to a rotation driving means, and the tubular support is revolved at a speed of 1 to 100 sec / cycle in association with rotation of the holder support.
delete The deposition apparatus of claim 1, further comprising a third target disposed in the deposition chamber and for supplying a third material to be deposited onto the tubular support surface.
The deposition apparatus according to claim 5, further comprising a shutter for shielding the third target, wherein the shutter is opened and closed by a driving means.
The deposition apparatus of claim 1, further comprising a vacuum pump for controlling the pressure in the deposition chamber.
delete The apparatus of claim 1, further comprising heating means for controlling the temperature of the tubular support, wherein the temperature of the tubular support is 300-600 ° C. using the heating means when material is deposited on the surface of the tubular support. Deposition apparatus, characterized in that to maintain a constant in the range.
delete The deposition apparatus of claim 1, wherein the holder is rotated by being connected to a rotation driving means, and the tubular support rotates at a speed of 1 to 100 sec / cycle in conjunction with rotation of the holder.

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