KR101861701B1 - Sputter equipment and method of manufacturing hydrogen separation membranes using the same - Google Patents

Abstract

According to an aspect of the present invention, there is provided a sputtering apparatus for depositing a vapor deposition metal on a substrate by generating a plasma between a target containing a vapor deposition metal and a substrate in a chamber, the sputtering apparatus comprising: A target gun module device formed radially on the side of the target gun module and including a plurality of target gun modules; A substrate holder formed inside the chamber; A substrate rapid heating module mounted on a lower portion of the substrate holder to control the temperature of the substrate; A substrate holder rotation adjusting device installed on a lower side of the chamber and controlling rotation of the substrate holder; A substrate holder height adjusting device for controlling the upward and downward movement of the substrate holder; A first main exhaust port formed in a side wall of the chamber and connected to a main exhaust valve for controlling the exhaust amount of the first vacuum pump to maintain the main exhaust atmosphere in the chamber; A second auxiliary exhaust port attached to a lower portion of the first main exhaust port and connected to a second exhaust valve for controlling an amount of exhaust of the second vacuum pump to perform an initial exhaust function in the chamber; A close exhaust pipe connected to the second vacuum pump through a close exhaust valve and connected to a lower side of the substrate holder to perform close exhaust of the substrate; And a control unit controlling each component of the sputtering apparatus to perform a sputtering process control; And a sputtering apparatus.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a sputtering apparatus and a hydrogen separation membrane using the same,

The present invention relates to a high-performance sputtering apparatus and a method for manufacturing a hydrogen separation membrane using the same.

Hydrogen energy is pollution-free clean energy, and it is a field of renewable energy. (1) low installation cost, (2) low installation space, (3) simple process configuration, (4) high hydrogen recovery rate, (5) continuous operation capability, (6) high purity hydrogen production (7) Hydrogen separation and purification process using hydrogen separation membrane is mainly used for advantages such as energy efficiency through simultaneous reaction and separation processes.

The hydrogen separation membrane is mainly formed of materials having various characteristics such as metals and ceramics. Typically, a dense hydrogen separation layer having no pores for selectively removing hydrogen and a porous support for supporting a very thin hydrogen separation layer .

The microstructure of the metal hydrogen separation membrane has a considerable influence on the hydrogen permeability and hydrogen selectivity of the hydrogen separation membrane, and a very dense and thin membrane is required to satisfy the hydrogen selectivity and hydrogen permeability requirements.

Generally, electroplating method and dry type sputter deposition method can be used for the coating method of the alloy metal.

Electrolytic plating may be preferred to dry sputter deposition, which facilitates control of process parameters and allows continuous multiple deposition in a vacuum environment because it involves wet and complex pretreatment processes.

In the case of such a conventional sputter deposition method, the step coverage can be lowered due to the linearity of the sputtered particles in the target, which may involve non-uniform deposition.

In addition, the thin film layer produced by the conventional sputtering method is formed by the pores of the columnar valley due to the columnar structures grown in the vertical direction on the surface of the support, The selectivity characteristic may be degraded.

For example, the metal thin film layers produced by the conventional sputtering method may have difficulty in producing a dense palladium alloy hydrogen separation membrane at a thin thickness even if a subsequent alloying heat treatment process is performed due to the pores of the columnar structure, In the case of the above thick film, it is possible to form a dense film by the alloying heat treatment process, but it may be difficult to commercialize it because the hydrogen permeability of the separation membrane is low.

Therefore, a high-performance sputtering apparatus capable of producing a thin film having improved step coverage and uniformity compared to a conventional sputtering apparatus is required for manufacturing and commercializing a hydrogen separation membrane.

Background art on the technique of the present invention is disclosed in Korean Patent Publication No. KR20115-0048901A.

Korean Patent Publication No. KR20115-0048901A (Sputtering Apparatus, Thin Film Deposition Method and Control Device)

The present invention provides a sputtering apparatus capable of producing a thin film having improved step coverage and uniformity.

It is still another object of the present invention to provide a high-performance sputtering apparatus capable of forming a uniform and dense metal alloy film on a porous substrate by controlling the substrate holder rotation and position control and efficiently controlling the exhaust acting on the deposition substrate .

It is still another object of the present invention to provide a substrate heating apparatus and a sputter process variable controlling apparatus for efficiently heating an evaporation substrate and a high functional sputtering apparatus capable of forming a uniform nano metal nucleus nucleus and a metal nano- Device.

It is still another object of the present invention to provide a substrate heating apparatus and a sputter process variable control apparatus capable of efficiently controlling the substrate holder rotation and position control and the exhaust acting on the deposition substrate and efficiently heating the deposition substrate, And a method for producing a hydrogen separation membrane by a palladium alloy using a sputtering apparatus.

The object of the present invention is not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood from the description of the detailed description.

According to an aspect of the present invention, there is provided a sputtering apparatus for depositing a vapor deposition metal on a substrate by generating a plasma between a target containing a vapor deposition metal and a substrate in a chamber, the sputtering apparatus comprising: A target gun module device formed radially on the side of the target gun module and including a plurality of target gun modules; A substrate holder formed inside the chamber; A substrate rapid heating module mounted on a lower portion of the substrate holder to control the temperature of the substrate; A substrate holder rotation adjusting device installed on a lower side of the chamber and controlling rotation of the substrate holder; A substrate holder height adjusting device for controlling the upward and downward movement of the substrate holder; A first main exhaust port formed in a side wall of the chamber and connected to a main exhaust valve for controlling the exhaust amount of the first vacuum pump to maintain the main exhaust atmosphere in the chamber; A second auxiliary exhaust port attached to a lower portion of the first main exhaust port and connected to a second exhaust valve for controlling an amount of exhaust of the second vacuum pump to perform an initial exhaust function in the chamber; A close exhaust pipe connected to the second vacuum pump through a close exhaust valve and connected to a lower side of the substrate holder to perform close exhaust of the substrate; And a control unit controlling each component of the sputtering apparatus to perform a sputtering process control; And a sputtering apparatus.

In addition, a substrate holder housing of a hexahedron is formed at a lower portion of the substrate holder, and the substrate rapid heating module is mounted inside the substrate holder housing.

A plurality of exhaust holes are formed in the substrate holder. The lower surface of the substrate holder housing is connected to a substrate holder supporting shaft tube passing through a lower surface of the chamber. The close exhaust pipe is connected to the support shaft tube, And is connected by a pipe.

Further, a gear or a belt pulley is mounted on the outer circumferential surface of the substrate holder support shaft tube, and is connected to a rotary shaft pulley of a substrate holder rotation control motor mounted on the movable base plate as a gear or a belt, and the control unit controls the substrate holder rotation control motor And controls rotation and rotation positions of the substrate holder.

In addition, a screw type flange bearing is mounted on one side of the moving base plate, the screw type flange bearing is screwed to a vertically formed linear screw shaft, and the screw type flange bearing is mounted on a lower side of the moving base plate The substrate holder height control motor is connected to the holder height control motor and is moved up and down while being rotated by the rotation of the substrate holder height control motor, and the control unit controls the height position of the substrate holder by controlling the substrate holder height control motor .

The first vacuum pump has a larger capacity than the second vacuum pump and is formed of a high vacuum pump. The throttle valve further includes a throttle valve for controlling the flow conductance between the first main exhaust port and the main exhaust valve, Wherein the first vacuum pump is equipped with a first self-exhaust valve for exhausting the inside of the vacuum pump, the first self-exhaust valve is connected to the second vacuum pump, and the control unit forms the initial vacuum atmosphere of the sputtering apparatus, Opening the second exhaust valve with the second vacuum pump activated, performing a first vacuum evacuation inside the chamber to a first vacuum state; Opening all of the exhaust valves in the chamber to open the first self-evacuating valve and operating the second vacuum pump for a predetermined time to perform self-evacuation and vacuum evacuation inside the first vacuum pump; Opening the second exhaust valve with the second vacuum pump in operation, performing a first vacuum evacuation inside the chamber to a first vacuum state; Closing the second exhaust valve, opening the main exhaust valve connected to the first vacuum pump, and performing a second vacuum evacuation until a set degree of vacuum is reached; Introducing a predetermined amount of reaction gas into the chamber using a gas injection unit and controlling the throttle valve to maintain the set chamber process pressure; And operating the target gun module by applying power to the substrate holder and simultaneously opening the close exhaust valve of the close exhaust pipe connected to the lower portion of the substrate holder to perform close contact and exhaustion of the substrate. And a control unit.

Furthermore, the primary vacuum exhaust is 5 (± 5%) × 10 - characterized in that the ³ torr, and said secondary vacuum exhaust is 5 (± 5%) × 10 -6 torr.

The target gun module device may further include a target gun forward shutter for blocking and opening the front of the target gun by a control rod to remove foreign substances to be adhered to the target and prevent mixing of different target materials .

Also, the substrate rapid heating module may include: a halogen lamp having a wavelength band of 800 to 1200 nm, which is arranged in a plurality of dots to generate a heat source; A semicircular reflector plated with gold and mounted on a lower portion of each of the plurality of halogen lamps; A temperature sensor for sensing the temperature of the lower portion of the substrate holder; Wherein the substrate holder is formed of quartz glass or pyrex glass, and is disposed at a focusing position of the reflection plate.

Further, the substrate holder housing is formed with a cooling passage through which the refrigerant circulates.

According to another aspect of the present invention, in the method for manufacturing a hydrogen separation membrane using the sputtering apparatus, the method for preparing a hydrogen separation membrane includes: preparing a porous nickel support used as a substrate; A surface modification step of treating the surface of the porous nickel support; A palladium nucleation step of forming nuclei of the palladium nanoparticles on the porous nickel support; Forming a palladium nanoside layer on the porous nickel support using the substrate rapid heating module; Forming a palladium alloy dense layer on which at least one metal layer for alloying selected from among palladium, gold, silver, copper and nickel alloys is deposited on the palladium nano-seed layer; The hydrogen separation membrane according to the present invention is a hydrogen separation membrane.

The surface modification step may include: a surface polishing step of smoothly polishing the size and uneven surface roughness and flatness of the macropores on the surface of the porous nickel support; To reduce the step difference between the polished surface and the polished surface of the polished porous nickel substrate, a slurry prepared by diluting YSZ 5 탆 powder or 100 nm particle size ceramic powder in water was applied to the surface of the polished support, A vacuum embedding step performed; Cleaning the buried porous nickel support with polyvinyl alcohol using a brush after the vacuum embedding step; Drying the cleaned porous nickel support at a temperature of 70 (賊 5%) 캜 for 2 (賊 5%) hours using a vacuum drier; And then subjected to a nitrogen purge, 1.0 (± 5%) × 10 - 3 torr initial pressure and 1.0 (± 5%) × 10 in the ^- in the process a pressure of ¹ torr 40 (± 5%) gives flowing a hydrogen gas of sccm , A plasma surface treatment to treat the porous nickel substrate with a plasma for 20 (± 5%) minutes at a discharge AC power frequency of about 13.56 (± 5%) MHz at room temperature and an AC power supply of 100 step; And a control unit.

The palladium nucleation step may include driving the first vacuum pump to form a process pressure set in the chamber, driving the second vacuum pump, opening the close exhaust valve, and exhausting the porous nickel support And the target gun module device is operated to perform sputtering of palladium. The distance between the target and the porous nickel support is fixed within a range of 30 to 50 mm, and a direct current power of 160 to 200 W, a direct current power of 15 , the adhesion of the close contact with the exhaust the exhaust while maintaining a chamber pressure of ³ torr ^- argon gas of ~ 20 sccm, 1.0 (± 5 %) × 10 -2 torr and then operate the plasma at a chamber pressure 1.0 (± 5%) × 10 pressure is ^{3.0 × 10 -4 ~ 8.0 × 10} -4 torr , and maintain a constant operating pressure in the range from 20 to 40 cho the porous nickel support the upper part of the diameter of 20 ~ 50nm size of Palladium for under the process conditions set to substrate temperature of room temperature It characterized in that for generating a nuclear particle.

The step of forming the palladium nanoside layer may include operating the substrate rapid heating module following the same process conditions of nucleating the palladium particles to heat the temperature of the porous nickel support to a predetermined temperature in the range of 200 to 400 ° C And a rapid heating step is further included to form the palladium nanoside layer.

Further, in the step of forming the palladium alloy dense layer, the distance between the target and the porous nickel support is fixed within a range of 50 mm to 100 mm, and the pressure in the chamber is set to 1.0 × 10 ^-3 to 1.0 × 10 ^-2 torr A local vacuum is formed at a constant process pressure in the range of 3.0 × 10 ^-4 to 8.0 × 10 ^-4 torr while the constant pressure is maintained, Wherein the dense layer is formed under a condition that a direct current power of the target gun module device is 100 to 120 W, an argon gas flow rate is a predetermined amount of 20 sccm to 30 sccm, and a temperature of the substrate holder is set to room temperature.

A sputtering apparatus according to an embodiment of the present invention is a sputtering apparatus which is capable of easily controlling the rotation of a substrate holder and moving up and down and is provided on a porous nickel support by constituent elements including a close- It is possible to efficiently form a uniform dense vapor deposition film as compared with conventional devices.

In addition, it is easy to control the precise fine adjustment of the sputter process parameters, so that an ultra-thin densified hydrogen separation membrane having superior functionality can be manufactured by an in-situ continuous sputtering process.

According to the hydrogen separation membrane manufacturing method using the sputtering apparatus according to an embodiment of the present invention, excellent hydrogen permeation and selectivity can be exhibited by manufacturing a dense hydrogen separation membrane having an ultra-thin uniformity.

In addition, according to the hydrogen separation membrane manufacturing method using the sputtering apparatus according to an embodiment of the present invention, the manufacturing process is simple and efficient compared with the conventional method, and the mass production and reproducibility of manufacturing on large area substrates are also excellent.

The hydrogen separation membrane manufactured by the hydrogen separation membrane production method using the sputtering apparatus according to an embodiment of the present invention can be used not only in the field of hydrogen purification but also in the hydrogen separation process, the reaction separation simultaneous process, the coal gasification combined- Capture and storage fields, and the like.

1 is a schematic view showing a sputtering apparatus according to an embodiment of the present invention.
2 shows a substrate holder rotation adjusting device and a height adjusting device of a sputtering apparatus according to the present invention.
3 is a view for explaining a structure of an exhaust control device according to an embodiment of the present invention.
4 is a view for explaining a target gun module device of a sputtering apparatus according to the present invention.
FIG. 5 shows an example of the arrangement angle of a plurality of target gun modules according to an embodiment of the present invention.
6 is a view for explaining a substrate rapid heating module according to an embodiment of the present invention.
7 is a scanning electron microscope and a transmission electron microscope image of a hydrogen separation membrane manufactured according to an embodiment of the present invention.
FIG. 8 shows a scanning electron microscope and a transmission electron microscope image of a hydrogen separation membrane manufactured using a conventional sputtering apparatus.
FIG. 9 is a graph showing the characteristics of the main structure, the dense membrane structure, and the hybrid structure of the hydrogen separation membrane manufactured according to an embodiment of the present invention.
FIG. 10 shows steps of a hydrogen separation membrane production method using a sputtering apparatus according to an embodiment of the present invention.
11 illustrates a process example for a surface modification step according to an embodiment of the present invention.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise.

In the present application, the term "include" Or 'have.' , Etc. are intended to designate the presence of stated features, integers, steps, operations, components, parts, or combinations thereof, may be combined with one or more other features, steps, operations, components, It should be understood that they do not preclude the presence or addition of combinations thereof.

In the present application, when a component is referred to as "comprising ", it means that it can include other components as well, without excluding other components unless specifically stated otherwise. Also, throughout the specification, the term "on" means to be located above or below the object portion, and does not necessarily mean that the object is located on the upper side with respect to the gravitational direction.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and particular embodiments are illustrated in the drawings and will be described in detail in the detailed description. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

The terms first, second, etc. are used to distinguish the various components in the present invention, and the components are not limited numerically by the terms.

Hereinafter, embodiments of a sputtering apparatus and a hydrogen separation membrane using the same according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. In the following description, The same reference numerals are assigned to the same elements and a duplicate description thereof will be omitted.

For the sake of convenience of explanation, the direction of each constitution is based on the direction shown in the figure. However, the description in this direction is only an example of the position and operation state of the component, and the sputter apparatus according to the present embodiment and the method for manufacturing the hydrogen separation membrane using the same are not limited.

Hydrogen energy is pollution-free clean energy, and it is a field of renewable energy. Hydrogen energy is important as an alternative energy source for depletion of fossil fuels and is suitable for environmentally friendly energy to prevent global warming.

For example, water generated when it is burned or converted to electricity is totally harmless to the environment and can be used again.

Hydrogen separation and purification processes using hydrogen separation membranes have been evaluated as the most promising technologies for producing high purity hydrogen.

The hydrogen separation membrane manufactured according to an embodiment of the present invention can perform the simultaneous reaction and separation processes, thereby making the process compact, increasing the thermal efficiency, and continuously separating the products to improve the reaction rate.

Hydrogen separation membranes containing alloys of non-porous palladium have high hydrogen selectivity in mixed gases and have excellent thermal, chemical and mechanical properties.

Such a non-porous membrane is poor in hydrogen permeability and is difficult to be commercialized.

Accordingly, a composite method of coating a thin palladium alloy film with a sputtering apparatus on a substrate formed of a porous support has been researched as an alternative.

The sputtering apparatus includes a sputtering apparatus for depositing the vapor deposition metal on a substrate by generating a plasma between a target including a vapor deposition metal and a substrate in a chamber,

However, according to the conventional method of producing a hydrogen separation membrane using a sputtering apparatus, a palladium alloy film coated on the porous support surface can be generated in an insufficient manner according to the pore state or surface roughness of the porous support surface, and pores and defects . In addition, the film layer is formed to be thick to some extent and exhibits low hydrogen selectivity and low permeability.

In order to solve the problems in the conventional sputtering apparatus and process, in one embodiment of the present invention, the power and target gun module unit, substrate holder rotation and height movement control unit, coherent exhaust unit, and temperature and pressure are efficiently and finely controlled The sputtering apparatus comprising:

There is also provided a process for producing a hydrogen separation membrane that produces a uniform, dense ultra-thin palladium alloy separation membrane on a porous support.

According to the method of manufacturing a hydrogen separation membrane by sputtering equipment according to an embodiment of the present invention, a large area hydrogen separation membrane having high permeability selectivity can be manufactured.

According to the method for producing a hydrogen separation membrane by sputtering equipment according to an embodiment of the present invention, a palladium nanoside layer is formed on a porous metal support using a high-performance sputter, and then a continuous in-situ sputtering process is performed, A hydrogen separation membrane can be produced.

The microstructure of the palladium alloy hydrogen separation membrane has a considerable influence on the hydrogen permeability and hydrogen selectivity of the hydrogen separation membrane, and a very dense and thin membrane is required in order to satisfy the high hydrogen selectivity and hydrogen permeability requirements.

The hydrogen separation membrane by the sputtering apparatus according to an embodiment of the present invention can improve the hydrogen selectivity and the hydrogen permeability at the same time.

Hereinafter, the structure and operation principle of a sputtering apparatus according to an embodiment of the present invention and the method for manufacturing a hydrogen separation membrane using the same will be described in detail with reference to the accompanying drawings.

1 is a schematic view showing a sputtering apparatus according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view illustrating a sputter apparatus according to an embodiment of the present invention. FIG.

1, a sputtering apparatus 1 according to the present invention includes a chamber 10, a plurality of target gun modules 111, 112, and 113 radially formed on an upper surface side of the chamber 10, A substrate holder 30 mounted in the chamber 10, a substrate rapid heating module 40 mounted on a lower portion of the substrate holder 30 to control the temperature of the substrate, A gas injection unit 21 for injecting gas into the chamber 10, a substrate holder rotation control unit 90 installed at a lower side of the chamber 10 for controlling rotation of the substrate holder 30, And a substrate holder height adjusting device 50 for controlling the upward and downward movement of the substrate holder 30.

In addition, the sputtering apparatus 1 according to an embodiment of the present invention includes an exhaust control device 60 for efficiently controlling the exhaust of the chamber and controlling the close exhaust of the substrate.

The exhaust control device 60 is connected to a main exhaust valve 61 which is formed on a side wall of the chamber 10 and controls the amount of exhaust of the first vacuum pump 71, A main exhaust port 61-1 and a second exhaust valve 63 connected to the lower portion of the first main exhaust port 61-1 and controlling the amount of exhaust of the second vacuum pump 72, A second auxiliary exhaust port 63-1 for performing an initial exhaust function in the substrate holder 30 and a second exhaust port 63-1 connected to the lower side of the substrate holder 30 via the second vacuum pump 72 and the close exhaust valve 64, And a close exhaust pipe (68) for performing close contact and exhaust of the substrate.

In an embodiment of the present invention, the first vacuum pump 71 has a larger capacity than the second vacuum pump 72 and is made of a high vacuum pump.

That is, since the second vacuum pump 72 has a smaller capacity than the first vacuum pump 71 and is formed of a low vacuum pump, the first vacuum pump 71 is driven to form an initial vacuum atmosphere So that a vacuum atmosphere can be formed economically and efficiently.

In addition, the second vacuum pump 72 performs a function of forming a local vacuum by performing close contact with the substrate holder 30, which is a feature of the present invention.

The sputtering apparatus 1 according to an embodiment of the present invention further includes a control unit that controls each of the components in accordance with the sputtering process so as to stably form a desired deposited layer on the substrate.

A substrate holder housing 33 having a hexahedron is formed at a lower portion of the substrate holder 30. A substrate rapid heating module 40 is mounted in the substrate holder housing 30 and a substrate 31 is disposed at an upper portion of the substrate holder 30.

According to an embodiment of the present invention, the substrate 31 may be a porous substrate.

According to one embodiment of the present invention, the substrate 31, which is the porous support, which is the subject of the sputtering process, is isolated from the outside by the chamber 10, and the chamber 10, during the sputtering process, to provide.

Here, the chamber 10 may be provided with a door (not shown) for allowing the substrate 31 to flow in and out of the chamber 10.

2 shows a rotation adjusting device and a height adjusting device of the substrate holder of the sputtering apparatus 1 according to the present invention.

2, the lower surface of the substrate holder housing 33 of the substrate holder 30 is connected to a substrate holder support shaft tube 47 passing through the lower surface of the chamber 10. [

That is, the inside of the substrate holder support shaft tube 47 includes the function of the close exhaust pipe 68.

The substrate holder 30 is rotated and vertically controlled according to the movement of the substrate holder support shaft tube 47.

The substrate holder support shaft tube 47 is mounted through the lower surface of the chamber 10 and a gear or belt pulley 95 is mounted on the outer circumferential surface of the substrate holder support shaft tube 47. The movable base plate 55 And is connected to the rotary shaft pulley of the substrate holder rotation control motor 96 as a gear or belt.

Therefore, the control unit (not shown) according to the embodiment of the present invention transmits the rotation control signal to the rotation control motor 96 to control the rotation to rotate the substrate holder supporting shaft tube 47, 30 can be controlled.

According to an embodiment of the present invention, the rotation control motor 96 may be a sub motor having a rotary speed reducer for precise rotational position control.

According to an embodiment of the present invention, the lower surface of the chamber through which the substrate holder support shaft tube 47 penetrates is held to maintain the vacuum hermeticity inside the chamber 10 due to the movement of the substrate holder support shaft tube 47 And a lower portion of the bellows tube 19 is connected to a bellows tube 91. The lower portion of the bellows tube 19 is connected to a magnetizable feed through seal 92 which keeps the airtightness due to the rotation and vertical movement of the substrate holder supporting shaft tube 47 by a magnetic field. ).

The bellows tube 91 makes it possible to precisely control the distance between the target and the substrate holder 30 while maintaining airtightness by contraction and expansion as the substrate holder support shaft tube 47 moves.

A screw type flange bearing 52 is mounted on one side of the moving base plate 55. The screw type flange bearing 52 is moved by screwing with a vertically formed linear screw shaft 53, Shaped flange bearing 52 is connected to a height control motor 51 mounted on the lower part of the moving base plate and is moved up and down while being rotated by the rotation of the substrate holder height control motor 51.

According to an embodiment of the present invention, the height control motor 96 may be a stepping motor whose rotation is controlled according to pulses for precise upper and lower position control.

The movable base plate 55 is mounted such that the sliding bushing 58 installed at the center thereof is slidably engaged with the sliding fixed shaft 57 so that the entire movable base plate 55 is horizontally And is moved up and down stably.

In other words, the sliding bushing 58 is configured such that one side of the movable base plate 55 is vertically moved in the up and down direction by the screw shaft 53, It plays a role of moving.

A control unit (not shown) according to an embodiment of the present invention transmits a height control signal to the height control motor 96 to control the rotation direction and the rotation amount, (The distance from the center of the target of the target gun to the surface of the substrate) for the uniform and dense deposition layer of the substrate by adjusting the height position of the substrate holder 30 Can be controlled.

The sputtering apparatus 1 having the high functionality described in FIGS. 1 and 2 according to an embodiment of the present invention includes a rotation adjusting device and a height adjusting device for performing the rotation amount and rotation position control of the substrate holder 30, The substrate rapid heating module 40 and the coherent exhaust device are used together with a substrate on which the sputtered target particles are rotated in the substrate holder in the course of the sputtering process, So that the uniformity of the thin film formed on the substrate can be improved by improving the step coverage of the porous substrate.

3 is a view for explaining a structure of an exhaust control device according to an embodiment of the present invention.

3, an exhaust control device 60 according to an embodiment of the present invention is mounted on a side wall of the chamber 10 and is connected to a first main exhaust port 61-1 inside the chamber 10 A main exhaust valve 61 for controlling main exhaust and a second exhaust port 63-1 mounted on a side wall of the chamber 10 and mounted on a lower portion of the first main exhaust 61-1 A second exhaust valve 63 that performs a primary evacuation function in the chamber 10 and is connected to the lower portion of the chamber 10 by a close exhaust pipe 68 at a lower portion of the substrate holder 30, And an exhaust control device 60 including a close exhaust valve 64 performing a close exhaust function of the lower portion of the substrate.

The high vacuum exhaust port 61-1 is connected by a first vacuum pump 71 and a main exhaust valve 61 and is disposed inside the chamber 10 in close proximity to the upper surface of the substrate holder 30 And is placed on the horizontal line.

A throttle valve 65 for controlling the flow conductance is further included between the first main exhaust port 61-1 and the main exhaust valve 61. [

The first vacuum pump 71 is equipped with a main exhaust valve 61 connected to the throttle valve 65 and a first self exhaust valve 62 for exhausting the inside of the first vacuum pump 71, The first self-discharge valve (62) is connected to the second vacuum pump (72).

Thus, the first main exhaust port 61-1 can be disposed on a horizontal line close to the substrate holder 30 to minimize the pressure gradient that may occur locally in the chamber 10 during the process.

The second auxiliary exhaust port 63-1 is connected by the second vacuum pump 72 and the second exhaust valve 63. [

The close exhaust pipe (68) is connected to the second vacuum pump (72) by a close exhaust valve (64).

The close exhaust pipe 68 is attached to the substrate holder supporting shaft tube 47 so that the rotatable flange 7 is connected to the flexible tube 66 and the substrate holder supporting shaft tube 47 without being affected by the rotation of the movable tube 66 ).

A plurality of exhaust holes are formed in the substrate holder 30 and a substrate holder supporting shaft tube 47 connected to the close exhaust pipe 68 is mounted on the substrate holder 30 using the characteristics of the porous substrate in the substrate made of the porous substrate. And is connected to the lower portion of the housing, it is possible to induce plasma condensation in the vicinity of the substrate by such a close-coupled exhaust pipe (68) to achieve uniform deposition on the porous substrate.

In other words, the constraint exhaust pipe 68 is connected through the substrate holder support shaft pipe 47, so that it is possible to perform close-contact exhaustion downwardly with respect to the substrate disposed above the substrate holder 30.

The process of controlling the control unit to form the initial vacuum atmosphere of the sputtering apparatus 1 according to an embodiment of the present invention is as follows.

First, the second opening the second exhaust valve 63 in a state of operating the vacuum pump 72, a first vacuum pump, a first vacuum (5 × 10 ^{- 3} torr) of the level to operate the chamber 10 to the Thereby performing the primary vacuum evacuation.

Next, all of the exhaust valves in the chamber 10 are closed, and the first self-evacuating valve 62 is opened and the second vacuum pump 72 is operated for a predetermined time, so that the self-evacuation and the first vacuum pump 71 Vacuum exhaust is performed.

Next, the second exhaust valve 63 operated for the low vacuum exhaust is closed and the main exhaust valve 61 connected to the first vacuum pump 71 is opened to set the secondary vacuum degree (5 × 10 ^-6 torr) And the second high vacuum exhaust is performed until it reaches.

Next, a certain amount of gas is introduced using the gas injection unit 21, and the flow conductance controlling throttle valve 65 is controlled to maintain the set chamber process pressure.

Thereafter, a plasma power source is applied to the target gun, and the target gun modules 111, 112, and 113 are operated and the close exhaust valve 68 of the close exhaust pipe 68 connected to the lower portion of the substrate holder 30 is opened, Exhaust.

According to the sputter apparatus 1 described in FIGS. 1 to 3 according to an embodiment of the present invention, the step coverage ratio characteristic of the deposited film deposited on the surface of the porous support, The uniform hydrogen separation membrane can be formed, and the exhaust process energy consumption can be economically operated according to the first and second vacuum exhaust processes.

4 is a view for explaining a target gun module apparatus 100 of a sputtering apparatus according to the present invention.

Referring to FIG. 4, the target gun module device 100 is radially mounted on the inside of the upper surface of the chamber 10 by a plurality of target gun modules 111, 112, and 113.

FIG. 5 illustrates an arrangement angle of a plurality of target gun modules 111, 112, and 113 according to an embodiment of the present invention.

5, the target gun module device 100 includes three target gun modules 111, 112, and 113 spaced 120 degrees from the top surface of the chamber 10 , And arranged to face the substrate holder 30 in a radial direction at a constant facing angle.

The target gun module 112 includes a yoke array 115 in which permanent magnets are arranged, a thick plate 116 to which a target is attached, a cooling water supply portion 118 to which cooling water is supplied, electric power And a supply unit 119.

The target gun module device 100 further includes a target gun front shutter 101 (not shown) for blocking and opening the front of the target gun by the control rod 102 to remove foreign substances to be adhered to the target, ).

In an embodiment of the present invention, the target gun module 100 may include three target gun modules 111, 112, and 113, but the target gun modules may be installed in five or more as needed .

The target gun module 112 induces a plasma discharge with the substrate on the substrate holder by the discharge power provided on the target surface, thereby sputtering the target material to deposit the target material on the substrate.

The target material may be mounted as a different material for each target gun module.

According to an embodiment of the present invention, palladium may be mounted on the target of the target gun module device 100, or palladium may be mounted on the first target of the first target gun module 111, 112 can be continuously or simultaneously co-sputtered in an in-situ manner by attaching a material for alloying to the palladium separation layer single layer and the metal lamination layer for a palladium alloy having a dense structure.

6 is a view for explaining a substrate rapid heating module according to an embodiment of the present invention.

According to one embodiment of the present invention, the substrate rapid heating module 40 is formed in a structure for maximizing rapid heating.

The substrate rapid heating module 40 is installed in the substrate holder housing 33 under the substrate holder 30.

According to an embodiment of the present invention, the substrate rapid heating module 40 includes a plurality of halogen lamps 41 arranged in a dot pattern for generating a heat source, a semicircular A temperature sensor 46-1 that senses the temperature of the substrate holder in the lower portion of the substrate holder and the temperature in the substrate temperature housing, and a lamp housing 43. [

The substrate holder support shaft 47 further includes a conduit and is connected to a halogen lamp power supply lead 45 and a temperature sensor 46-1 connected to the halogen lamp 41 using the conduit And a temperature sensing control line 46 for sensing the temperature in the lamp housing 43.

According to an embodiment of the present invention, the substrate rapid heating module 40 employs a halogen lamp 41 capable of rapid temperature control and non-contact heating as compared with other heat sources for heating a substrate.

In addition, the substrate rapid heating module 40 is configured to rapidly and uniformly heat the halogen lamps 41 having a high emissivity in a wavelength band of 800 to 1200 nm by densely arranging them in a dot pattern.

Further, peripheral devices are disposed in consideration of the focal distance (f = 20 mm) and the distance to the condensing focus position according to the characteristics of the halogen lamp 41 and the reflection plate 42 to minimize heat transfer to peripheral devices, The substrate holder is positioned at the highest position to maximize heating efficiency.

Also, according to an embodiment of the present invention, the bottom surface of the halogen lamp reflector 42 may be plated with gold (Au) to induce total reflection in a semi-circular structure.

Further, in order to lower the temperature, which is an important factor in the early stage of nano-nucleation in the process, a cooling passage is formed in the substrate holder housing 33 or the lamp housing 43 to cool the substrate by circulating the coolant .

In addition, the substrate holder 30 is made of quartz glass or pyrex glass for preventing secondary contamination of the plating surface that may occur during sputter deposition and for maintaining the light transmittance of the halogen light source.

The substrate holder 30 is formed so as to be hermetic with the substrate holder housing 33 except for a plurality of closely-coupled exhaust holes 39 in which the porous substrate is located.

According to the sputter apparatus 1 having high functionality described in Figs. 1 to 6 according to an embodiment of the present invention, by the rapid heating of the substrate of the substrate rapid heating module 40 in a high vacuum state in the chamber 10 The horizontal growth of the palladium nanoparticle nuclei is generated and a uniform palladium nanoside layer can be formed.

Next, a method of manufacturing a hydrogen separation membrane using the sputtering apparatus according to an embodiment of the present invention will be described.

In general, sputtering processes are basically plasma generation in a vacuum state and sputtering phenomena of a target.

In accordance with one embodiment of the present invention, a preliminary test for plasma conditions was conducted as follows to primarily observe significant plasma generation prior to sputter deposition. The TS (Target to Substrate) distance was kept constant at 50 mm, and the plasma formation and the degree of vacuum were measured according to the argon gas flow rate change.

Table 1 shows the plasma formation and the degree of vacuum measurement according to the argon gas flow rate change.

target  : Palladium variable Presence or absence of discharge T-S distance: 50mm Pressure (Torr) Ar ( sccm ) One 6.0x10 ^-One 500 ○ 2 2.5x10 ^-One 420 ○ 3 9.0x10 ^-2 260 ○ 4 6.0x10 ^-2 215 ○ 5 3.0x10 ^-2 170 ○ 6 2.0x10 ^-2 20 ○ 7 9.5x10 ^-3 20 ○ 8 7.5x10 ^-3 20 ○ 9 5.5x10 ^-3 20 ○ 10 3.5x10 ^-3 20 ○ 11 1.5x10 ^-3 20 ○ 12 8.5x10 ^-3 20 ○ 13 7.0x10 ^-4 20 ○ 14 5.0x10 ^-4 20 ○ 15 4.9x10 ^-4 19 ○ 16 4.5x10 ^-4 18 ○ 17 4.2x10 ^-4 17 ○ 12 3.7x10 ^-4 15 ○ 13 3.3x10 ^-4 14 ○ 14 2.9x10 ^-4 13 ○ 15 2.3x10 ^-4 12 ○ 16 1.8x10 ^-4 11 ×

Referring to Table 1, as the flow rate of argon gas is changed from 500 sccm (cm ³ / min) to 20 sccm, the degree of vacuum in the chamber is reduced from 6.0 × 10 ^-1 torr to 2.0 × 10 ^-2 torr. The vacuum degree 1.0 × 10 ^-3 torr, but plasma is not formed, the argon flow rate in the plasma formed 20sccm, and a degree of vacuum 2.0 × 10 ^-2 torr is maintained the plasma even by lowering the degree of vacuum to 5.0 × 10 ^-4 torr.

After lowering the argon flow rate to less than 20sccm degree of vacuum it is lowered and further, 2.3 × 10 in an argon flow rate of 12sccm ^- plasma is maintained at a high vacuum of ⁴ torr.

1.8 × 10 in an argon flow rate of 11sccm ^{- 4} torr in a vacuum to form a plasma, but does not appear to occur.

Therefore, it is shown that the plasma can be maintained even under a high vacuum of 2.0 x 10 ^-4 torr by the close-coupled exhaust apparatus of the sputter apparatus 1 according to the embodiment of the present invention and the substrate holder up and down movement regulating apparatus.

The sputter apparatus 1 according to an embodiment of the present invention can increase the mean free path of the particles emitted from the target under a high vacuum of 2.0 × 10 ^-4 torr to form uniform and fine nanoparticle nuclei on the porous substrate have.

The method of manufacturing an ultra thin film hydrogen separation membrane using the sputter apparatus 1 according to an embodiment of the present invention includes steps of forming a palladium nanoside layer by maximizing palladium fine uniform nucleation and forming palladium on the nanoside layer continuously And a densified layer forming step of uniformly and densely depositing the layer.

The process conditions of the high-performance sputter for forming the palladium nanoside layer according to an embodiment of the present invention are as follows.

The distance between the sputter target and the substrate is set to 50 (± 5%) mm or less. The direct current power is controlled to 160 to 200 W, and the argon gas supply amount is controlled to 15 to 20 sccm. In addition, 1.0 (± 5%) × 10 -2 torr and then operate the plasma at a chamber pressure 1.0 (± 5%) × 10 - 3 torr so while maintaining a low chamber pressure of 7.0 (± 5%) × 10 -4 torr The exhausting device is operated by the process pressure of.

According to one embodiment of the present invention, palladium sputter deposition under conditions set at room temperature induces nucleation of palladium particles in the number of tens to nano-size on the top of the porous metal support.

Further, when the substrate is rapidly heated by using the halogen lamp substrate rapid heating module 40 while keeping the local high vacuum at the bottom of the substrate while continuously setting the degree of vacuum of the main chamber, the uniformly nucleated tens of nano- Of palladium particles are uniformly formed by horizontal growth, and a palladium nanoside layer having an excellent step coverage can be formed.

According to an embodiment of the present invention, when a substrate is rapidly heated using a substrate rapid heating module including a halogen lamp, the substrate is instantaneously heated to about 300 to 400 ° C., and horizontal growth of uniformly formed palladium nuclei occurs, A nano seed layer is formed.

According to one embodiment of the present invention, the mean free path of the palladium particles emitted from the target by rapid heating and high power and high vacuum is increased, and the palladium ad surface diffusion of atoms, horizontal growth of palladium particles, as well as horizontal growth of palladium clusters due to increased reactivity of nanoparticles.

In addition, a nano seed layer of a dense palladium thin film of several tens of nanometers is formed continuously by repeating very fine particle deposition and growth.

In addition, when a dense palladium nanoside layer is formed on the surface of the porous nickel substrate, deposition of a dense palladium thin film on the palladium nanoside layer is facilitated by the same substrate effect.

According to an embodiment of the present invention, when a palladium nanoside layer is formed on the surface of a porous nickel support, a TS distance of 80 (± 5%) mm, a substrate temperature of room temperature, 1.0 (± 5%) × 10 ^-3 torr , A dense palladium thin film as shown in FIG. 6 (a) is formed under the sputtering conditions of a process pressure of 120 W, a direct current power of 120 W and an argon flow rate of 20 (± 5%) sccm.

7 is a scanning electron microscope and a transmission electron microscope image of a hydrogen separation membrane manufactured according to an embodiment of the present invention.

Referring to FIG. 7, the structure of the dense and uniformly formed hydrogen separation membrane can be seen.

FIG. 8 shows a scanning electron microscope and a transmission electron microscope image of a hydrogen separation membrane manufactured using a conventional sputtering apparatus.

The sputtering apparatus 1 having high functionality according to an embodiment of the present invention has an exhaust control device 60 including a close exhaust, a substrate rapid heating module 40, And a high-functionality configuration for the substrate holder rotation and height adjustment arrangement to be adjusted.

Using conventional sputtering equipment, deposition was carried out on the surface of a porous nickel support with process conditions of the same conditions: a TS distance of 80 mm, a substrate temperature of room temperature, a process pressure of 1.0 × 10 -2 torr, a direct current power of 80 W and an argon flow rate of 30 sccm As a result, as shown in FIG. 8, it was possible to obtain a form grown as a rough columnar-shaped palladium layer.

The palladium separation layer grown as described above does not exhibit dense surface microstructure due to macropores formed by the columnar valley and surface roughness, and thus a large number of pores are present on the surface. As a result, the selectivity of the hydrogen separation membrane is lower than that of the hydrogen separation membrane according to the embodiment of the present invention.

FIG. 9 is a graph showing the characteristics of the main structure, the dense membrane structure, and the hybrid structure of the hydrogen separation membrane manufactured according to an embodiment of the present invention.

The sputtering apparatus 10 according to an embodiment of the present invention can finely and precisely adjust the process parameters of the substrate temperature, the process pressure, the DC power source, and the TS distance by the characteristic elements described in Figs. 1 to 6, 9, separation membranes of columnar structure, dense membrane structure, and hybrid membrane (composite membrane of dense membrane structure and columnar structure) can be customized according to the use of the product.

Therefore, by applying the hydrogen separation membrane manufactured by the sputtering apparatus 1 having the high functionality described in FIGS. 1 to 6 according to an embodiment of the present invention and the manufacturing method using the same, it is possible to provide a high hydrogen permeability, It is easy to manufacture hydrogen for separation, high permeability and selectivity, so that the applicability of hydrogen can be maximized.

The hydrogen separation membrane manufactured by the sputtering apparatus 1 having high functionality according to an embodiment of the present invention is made of a palladium alloy film excellent in selective separation function of hydrogen and the hydrogen permeability and selectivity can be improved simultaneously So that it has a thin and dense microstructure.

FIG. 10 shows steps of a hydrogen separation membrane production method using a sputtering apparatus according to an embodiment of the present invention.

Referring to FIG. 10, a porous nickel support preparation step 210 is first performed as a substrate.

The porous metal support of the palladium or palladium alloy hydrogen separation membrane according to an embodiment of the present invention employs a porous nickel support in the form of a disc having a diameter of 1 inch or 2 inches.

In order to deposit a very thin hydrogen separation layer of a few microns thick on the porous nickel support, a surface modification step 220 is performed on the prepared porous metal support.

11 illustrates a process example for a surface modification step according to an embodiment of the present invention.

Referring to FIG. 11, in the surface modification step of the porous metal support, a surface polishing step 221 is first performed.

In order to control the uneven surface roughness and flatness and the size of the macropores, the surface polishing step 221 is first performed to smoothly maintain the size and uneven surface roughness and flatness of the macropores on the surface of the porous nickel support.

The surface polishing step 221 is performed such that the porous nickel support is fixed to the substrate holder of the automatic polishing machine capable of uniformly controlling the pressure and uniform rotation, and then the polishing part of the support and the polishing pad are always parallel and uniformly polished. Thereby minimizing the influence of the irregular wear.

The irregular waviness generated in the surface polishing step 221 causes polishing of relatively large particles, which causes scratches on the surface of the support or lowers the uniformity of the surface. Such irregularities may cause formation of dense and uniform hydrogen separation layers, or surface pores in the production of thin separation membranes of hydrogen separation layers.

According to an embodiment of the present invention, the abrasive paper is made of SiC Paper # 400 to # 4,000, and polishing is performed by adjusting process parameters such as pressure, RPM, and polishing time to remove foreign substances from the surface of the porous nickel substrate, The size, roughness and flatness are performed to reach the set point.

After the surface polishing step 221, a vacuum embedding step 222 is performed secondarily.

In a vacuum embedding step 222 according to an embodiment of the present invention, pores are selectively formed on the surface of the polished porous nickel substrate to reduce the stepped surface of the pores with YSZ 5 mu m, submicron, The slurry prepared by diluting the ceramic powder with DI water (DeIonize water) is applied to the surface of the polished support to perform embedding.

In the vacuum embedding step 222, a porous nickel support is mounted on a module connected to a vacuum pump to selectively uniformly fill ceramic pores in the macropores of the surface remaining after polishing, and then, using the YSZ powder, The slurry prepared separately is applied to the surface several times in order of large particle size, and then sucked into a vacuum pump and uniformly buried, thereby minimizing the step difference between the polished surface and the pores to Ra = 0.05 μm.

Further, since the buried powder is buried in the pores sequentially by the pressure flow by performing the vacuum embedding step (222), it is easier and more reproducible than the conventional powder embedding method.

After the vacuum embedding step, a cleaning step 223 and a drying step 224 are performed.

In the cleaning step 223, the polyvinyl alcohol solution is cleaned with a brush to clean impurities and foreign substances that may be generated by the vacuum embedding step.

After the cleaning step 223, a drying step 224 is carried out using a vacuum dryer at a temperature of 70 (± 5%) ° C for 2 (± 5%) hours.

After the drying step 224, a plasma surface treatment step 225 is performed.

The plasma surface treatment step 225 is performed for impurity removal and surface activation on the porous nickel support surface.

One implementation step the plasma surface treatment according to an embodiment of the present invention 225. In After being subjected to nitrogen purging, 1.0 (± 5%) × 10 - 3 torr initial pressure and 1.0 (± 5%) × 10 ^{in-process 1} torr (± 5%) sccm of hydrogen gas at a pressure of about 13.56 (± 5%) MHz at room temperature and 20 (± 5%) minutes of AC power source of about 100 W at room temperature, The surface of the support is treated with a plasma.

After the surface modification step (220) of the porous metal support, a palladium particle nucleation step is performed on the porous metal support.

The method for producing a hydrogen separation membrane according to an embodiment of the present invention is a method for manufacturing a hydrogen separation membrane according to an embodiment of the present invention, which uses a sputtering apparatus 1 having high functionality according to an embodiment of the present invention, Silver, copper, and nickel is used as an alloy metal to continuously produce a palladium alloy hydrogen separation layer.

The palladium alloy hydrogen separation layer according to an exemplary embodiment of the present invention may be prepared by first performing a nucleation step 230 of a palladium particle and a step 240 of forming a palladium nanoside layer and then continuously forming a palladium alloy on the nanoside layer And a dense layer forming step 250 of palladium alloy forming a dense layer.

First, in the palladium nucleation step 230, the control unit of the high-performance sputtering apparatus 1 according to an embodiment of the present invention controls the substrate holder height adjusting unit 50 to adjust the TS (Target to Substrate) distance to 30 And the surface-modified porous substrate is placed on the substrate holder 30. The substrate holder 30 is provided with a porous support.

First, the first vacuum pump is driven to form the process pressure set in the chamber 10, the second vacuum pump 72 is driven, and the close exhaust valve 64 is opened to perform close exhaust to the porous support, And the target gun module device 100 is operated to perform sputtering of palladium.

The process conditions in the palladium nucleation step 230 were as follows: a plasma was operated at a DC power of 160 to 200 W, an argon gas of 15 to 20 sccm, a 1.0 (± 5%) × 10 ^-2 torr chamber pressure, %) × 10 ^-3 torr, while maintaining a constant process pressure in the range of 3.0 × 10 ^-4 to 8.0 × 10 ^-4 torr at the close contact exhaust pressure and under a condition set at a substrate temperature of room temperature To produce 20 to 50 nm diameter palladium particle nuclei on top of the surface-modified porous support for 20 to 40 seconds.

The preferred process conditions in the palladium nucleation step 230 are 1.0 (± 5%) sccm of argon gas, 1.0 (± 5%) × 10 ^-2 torr chamber pressure and 1.0 The chamber pressure is maintained at 10-3 torr while the tight exhaust pressure is set to 7.0 (± 5%) × 10 ^-4 torr and the chamber temperature is set to 30 (± 5%) seconds under the condition set at the room temperature Can be applied.

That is, in a state in which the chamber vacuum degree of the constant pressure by the first vacuum pump is maintained, the close vacuum by the second vacuum pump is operated on the lower part of the substrate on which the porous support is placed so that the local vacuum (7.0 (± 5%) × 10 ^-4 torr to keep the palladium particles concentrated on the surface of the porous support.

Accordingly, in one embodiment of the present invention, the mean free path of the sputtered particles in the target is higher than the general sputtering process pressure using the conventional sputtering apparatus 1 under the above vacuum condition, thereby uniformly forming fine nuclei of nanoparticles .

Following the palladium nucleation step 230, a step 240 of forming a palladium nanoside layer is performed.

The step 240 of forming a palladium nanoside layer further includes the step of operating the substrate rapid heating module 40 following the same process conditions of the palladium particle nucleation step 230.

In the substrate rapid heating module 40 according to an exemplary embodiment of the present invention, a halogen lamp having a wavelength band energy of 800 to 1200 nm and a focal length (f = 20 mm) is used, and the core of the palladium particles, The palladium nanoside layer having a thickness of 200 to 300 nm is formed by heating at a temperature ranging from 200 to 400 ° C to a constant temperature.

According to an embodiment of the present invention, a peripheral device considering the distance to the condensing focus position is designed, and the porous nickel support is positioned at the position where the condensing energy is highest.

According to an embodiment of the present invention, when nuclei of palladium nanoparticles are formed, the substrate rapid heating module 40 installed at the lower end of the substrate holder 30 is operated to quickly heat the substrate on which the porous nickel substrate is placed, The palladium nanocrystals are formed in a horizontal growth direction, thereby forming a palladium nanoside layer having excellent step coverage of the surface.

According to one embodiment of the present invention, step coverage can be reduced due to the fine pores and steps of the remaining porous nickel support and the linearity of the sputtered particles in the target of the target gun module even after surface modification, (40)? The step coverage characteristic can be improved by forming a dense nano seed layer by horizontal growth of nanocrystal particles.

A step 240 of forming a palladium nanoside layer followed by a step 250 of forming a palladium alloy dense layer is performed.

The process conditions of the palladium alloy dense layer forming step 250 are set such that the TS distance is set within a range of 50 mm to 100 mm and the process pressure in the chamber 10 is set to 1.0 × 10 ^-3 to 1.0 × 10 ^-2 torr, while maintaining a constant pressure of the second driving the vacuum pump 72 and close to opening the exhaust valve 64, the exhaust in close contact with the porous nickel support, the palladium nano-oxide layer is formed ^{(3.0 × 10 -4 ~ 8.0 ×} 10 - ^A constant process pressure in the range of ⁴ torr) to form a local vacuum, and the target gun module device 100 is operated to perform sputtering of the palladium alloy.

At this time, palladium and gold, silver, and silver are deposited on the palladium nano-seed layer under the conditions that the DC power of the target gun module 100 is 100 to 120 W, the argon gas flow rate is 20 sccm to 30 sccm and the temperature of the substrate holder is room temperature. At least one metal layer for alloying selected from alloy metals such as copper, nickel and the like is deposited.

In a preferred embodiment of the present invention, following step 240 of forming a palladium nanoside layer, a target to substrate distance 80 (± 5%) mm, 120 (± 5%) mm in the palladium alloy dense layer formation step 250, %) W of the target gun module device 100, a process pressure of about 1.0 (± 5%) × 10 ^-3 torr of chamber pressure, and a substrate temperature of room temperature of about 20 sccm (5%) ㎛ thin film and dense hydrogen separation membranes were fabricated by the sputtering process under the condition of 15 (± 5%) minute.

The palladium alloy separation layer according to one embodiment of the present invention can be formed by precise fine adjustment of the sputtering process parameters by the above-described components of the apparatus described in Figures 1 to 6 to provide a compact structure, a porous structure or a hybrid (dense quality + Porous). ≪ / RTI >

According to one embodiment of the present invention, when the nano-seed layer is formed on the surface-modified porous nickel substrate, even if the nano-seed layer is relatively sputtered, The deposition of a continuous dense palladium thin film can be facilitated.

According to an embodiment of the present invention, a dense-film sputtering process is performed on the palladium nanoside layer, and a total of 6 탆 thick palladium and one alloy metal selected from gold, silver, copper, Multiple coatings are formed.

The nano seed layer manufacturing process and the dense membrane manufacturing process can produce a dense hydrogen separation layer by inducing dense thin film growth even by a dense film sputtering process relatively relaxed by the effect of the same kind of substrate of the initial nano seed layer The step coverage characteristic is excellent and a dense separation layer having no pores on the surface of the hydrogen separation layer can be formed.

After the palladium alloy dense layer formation step 250, a heat treatment step 260 is performed.

After the sputter coating processes of the hydrogen separation membrane are completed, the substrate rapid heating module 40 according to an embodiment of the present invention is operated to set the pressure in the chamber 10 in the chamber 10 to 5.0 (± 5%) × 10 ^In order to densify the surface of the hydrogen separation membrane formed in the dense layer formation step 250 of the palladium alloy in a high vacuum of ^-6 torr, a heat treatment process is performed at a temperature of 500 to 700 ° C for 5 to 20 minutes.

According to one embodiment of the present invention, the surface densification and the interfacial adhesion between the deposition layer and the porous support are improved through the heat treatment step (260).

One; Sputtering device
10: chamber
21:
30: substrate holder
33: substrate holder housing
39: Exhaust ball
40: Rapid heating module
41: Halogen lamp
42: reflector
43: Lamp housing
46-1; temperature Senser
47: substrate holder support shaft tube
50: substrate holder height adjustment device
60: Exhaust control device
61: Main exhaust valve
61-1 1st main exhaust port
62: first self-discharge valve
63-1: Second auxiliary exhaust
63: Second exhaust valve
64: close exhaust valve
65: Throttle valve
68: close exhaust pipe
71: first vacuum pump
72: Second vacuum pump
100: Targeted modular unit
101: Target gun forward shutter
102: Control Load
111, 112, 113: target gun module

Claims (15)

delete delete delete delete delete delete delete delete delete delete A method for manufacturing a hydrogen separation membrane using a sputtering apparatus for generating a plasma between a target containing a metal for vapor deposition in a chamber and a substrate to deposit the metal on the substrate,
The sputtering apparatus includes:
A target gun module device radially formed on an upper surface side of the chamber and including a plurality of target gun modules;
A substrate holder formed inside the chamber;
A substrate rapid heating module mounted on a lower portion of the substrate holder to control a temperature of the substrate;
A substrate holder rotation adjusting device installed on a lower side of the chamber and controlling rotation of the substrate holder;
A substrate holder height adjusting device for controlling the upward and downward movement of the substrate holder;
A first main exhaust port formed in a side wall of the chamber and connected to a main exhaust valve for controlling the exhaust amount of the first vacuum pump to maintain the main exhaust atmosphere in the chamber;
A second auxiliary exhaust port attached to a lower portion of the first main exhaust port and connected to a second exhaust valve for controlling the exhaust amount of the second vacuum pump to perform an initial exhaust function in the chamber;
A close exhaust pipe connected to the second vacuum pump through a close exhaust valve and connected to a lower side of the substrate holder to perform close exhaust of the substrate; And
A control unit controlling each component of the sputtering apparatus to perform a sputtering process control; , ≪ / RTI &
The substrate rapid heating module includes:
A halogen lamp having a wavelength band of 800 to 1200 nm arranged in a plurality of dots generating a heat source;
A semicircular reflector plated with gold and mounted on a lower portion of each of the plurality of halogen lamps; And
A temperature sensor for sensing the temperature of the lower portion of the substrate holder; / RTI >
Wherein the substrate holder is disposed at a converging focus position of the reflection plate,
In the hydrogen separation membrane production method,
Preparing a porous nickel substrate for use as the substrate;
A surface modification step of treating the surface of the porous nickel support;
A palladium nucleation step of forming nuclei of the palladium nanoparticles on the porous nickel support;
Forming a palladium nanoside layer on the porous nickel support using the substrate rapid heating module; And
Forming a palladium alloy dense layer on which at least one metal layer for alloying selected from among palladium, gold, silver, copper and nickel alloys is deposited on the palladium nano-seed layer; Wherein the hydrogen permeable membrane is a membrane membrane.
12. The method of claim 11,
In the surface modification step,
A surface polishing step of smoothly polishing the size and uneven surface roughness and flatness of the macropores on the surface of the porous nickel support;
To reduce the step difference between the polished surface and the polished surface of the polished porous nickel substrate, a slurry prepared by diluting YSZ 5 탆 powder or 100 nm particle size ceramic powder in water was applied to the surface of the polished support, A vacuum embedding step performed;
Cleaning the buried porous nickel support with polyvinyl alcohol using a brush after the vacuum embedding step;
Drying the cleaned porous nickel support at a temperature of 70 (賊 5%) 캜 for 2 (賊 5%) hours using a vacuum drier; And
After being subjected to nitrogen purging, 1.0 (± 5%) × 10 -3 torr initial pressure and 1.0 (± 5%) gives flowing a hydrogen gas of 40 (± 5%) sccm at process pressures of × 10 ^-1 torr, A plasma surface treatment step of treating the porous nickel substrate with a plasma for 20 (± 5%) minutes at a discharge AC power source frequency of 13.56 (± 5%) MHz at room temperature and an AC power source of 100 (± 5%) W; Wherein the hydrogen permeable membrane is a membrane membrane. 12. The method of claim 11,
The palladium nucleation step comprises:
Driving the first vacuum pump to form a set process pressure in the chamber, driving the second vacuum pump, opening the close exhaust valve and venting the porous nickel support to form a local vacuum, The target gun module device is operated to perform sputtering of palladium,
The distance between the target and the porous nickel substrate was fixed within a range of 30 to 50 mm and a plasma was generated at a DC power of 160 to 200 W, an argon gas of 15 to 20 sccm, and a chamber pressure of 1.0 (± 5%) × 10 ^-2 torr after operating 1.0 (± 5%) × 10 - while maintaining a chamber pressure of ³ torr, close the exhaust pressure of the exhaust in close contact maintains a constant process pressure of ^{3.0 × 10 -4 ~ 8.0 × 10} -4 torr range, Wherein the palladium particle nuclei having a diameter of 20 to 50 nm are formed on the porous nickel support for 20 to 40 seconds under a process condition set at a substrate temperature of room temperature. 14. The method of claim 13,
The step of forming the palladium nanoside layer comprises:
Further comprising a rapid heating step of operating the substrate rapid heating module following the same process conditions as the nucleation of the palladium particles to heat the temperature of the porous nickel support to a constant temperature in the range of 200 to 400 ° C., Is formed on the surface of the substrate (1). 12. The method of claim 11,
In the palladium alloy dense layer forming step,
Wherein a distance between the target and the porous nickel support is fixed within a range of 50 mm to 100 mm and the pressure in the chamber is maintained at a constant pressure in the range of 1.0 × 10 ^-3 to 1.0 × 10 ^-2 torr, Forming a local vacuum at a predetermined process pressure in the range of 3.0 × 10 ^-4 to 8.0 × 10 ^-4 torr and operating the target gun module device to perform sputtering of the palladium alloy,
Wherein the dense layer is formed under a condition that a DC power of the target gun module device is in a range of 100 to 120 W, a flow rate of an argon gas is in a range of 20 to 30 sccm, and a temperature of the substrate holder is set to a room temperature.

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