KR101492938B1 - Solid Oxide Fuel Cell comprising multilayer electrode and preparation method thereof - Google Patents

Abstract

When the solid oxide fuel cell according to the present invention is applied to a semiconductor or a manufacturing process of a display, it can be applied to a semiconductor or a display with a fine structure. In spite of this fine structure, the efficiency of the solid oxide fuel cell is excellent. In addition, since the multilayer thin film structure increases the ion conductivity, the internal resistance of the battery is reduced, thereby increasing the output of the solid oxide fuel cell. In addition, there is an effect of facilitating the large-scale mounting by preventing electrical short-circuiting due to defects during the large-area mounting. In addition, the multilayer thin film portion can be peeled off from the Si or glass substrate by a lift-off process and adhered to another flexible material, thereby realizing a low-cost flexible fuel cell.

Description

TECHNICAL FIELD [0001] The present invention relates to a solid oxide fuel cell including a multilayer thin film electrode and a manufacturing method thereof,

The present invention relates to a solid oxide fuel cell including a multilayer thin film electrode and a method of manufacturing the same.

Fuel cells are environmentally friendly energy cells that convert the chemical energy generated by the oxidation of fuel directly into electrical energy. The feature is that the reactants are continuously supplied from the outside and the reaction products are continuously removed out of the system.

The most typical fuel cell is a hydrogen-oxygen fuel cell, a high temperature type molten carbonate fuel cell, and a solid electrolyte fuel cell that generates electricity with higher efficiency.

In particular, a solid oxide fuel cell (SOFC) using a solid oxide such as zirconium oxide or ceria as an electrolyte generally operates at a high temperature of 700 to 1,000 DEG C and oxidized ions are conducted in the electrolyte, Hydrogen, as well as hydrocarbons such as methane and butane, and liquid fuels such as methanol, can generate electricity by electrochemically reacting with oxygen in the air. Among the various fuel cells, the power generation efficiency is the highest, and the energy conversion efficiency of the entire system can be further increased by effective utilization of the high-temperature waste heat.

On the other hand, such a solid oxide fuel cell can be introduced into a semiconductor or a display production process. However, the solid oxide fuel cell can be introduced efficiently because it has a fine-sized structure due to a sophisticated process due to the characteristics of a small-sized semiconductor or display. Particularly, in the case of a fuel cell electrode, there is a separation plate between the anode and the cathode. The presence of such a separation plate limits the microstructure of the solid oxide fuel cell, making it difficult to apply the solid oxide fuel cell to a semiconductor or a display. This problem also causes a problem of limiting the microstructure of the cell composed of the anode, the cathode and the separator. This also causes a problem that it is more difficult to form a stack with a plurality of cells in order to increase the efficiency.

As a prior art document for improving such a problem, Korean Patent Laid-Open No. 10-2009-0119187 (Patent Document 1) for a package including a fuel cell, a manufacturing method thereof, and a card and a system including a package is disclosed. Specifically, at least one semiconductor chip in a package capable of high integration, and at least one fuel cell disposed on the at least one semiconductor chip and electrically connected to the at least one semiconductor chip. However, the above Patent Document 1 also has a problem that the technique of applying the electrode of the solid oxide fuel cell to the semiconductor process with a microstructure is not disclosed.

Patent Document 1. Korean Patent Laid-Open No. 10-2009-0119187

It is an object of the present invention to provide a solid oxide fuel cell having excellent voltage / output even when applied to a semiconductor or a display manufacturing process. In particular, it is possible to provide a solid oxide fuel cell with a fine structure even when applied to a semiconductor or a display manufacturing process, and to provide a solid oxide fuel cell having excellent efficiency and a manufacturing method thereof.

According to an aspect of the present invention, there is provided a solid oxide fuel cell comprising:

A silicon wafer or a glass substrate coated with a thin film of SiO or SiN on its upper surface is located at the bottom;

A support layer is disposed on the SiO or SiN thin film;

A metal catalyst layer is adhered and disposed on the other surface of the support layer in contact with the SiO 2 or SiN thin film;

A multilayer thin film type electrode is attached to the other surface of the metal catalyst layer in contact with the support layer.

A method of manufacturing a solid oxide fuel cell according to another aspect of the present invention includes:

1) depositing and coating a thin film of SiO or SiN on a silicon wafer or a glass substrate;

2) forming a support layer on the deposited SiO or SiN thin film;

3) depositing a metal catalyst layer on the other surface of the surface of the support layer where the SiO 2 or SiN thin film is in contact with the support layer;

4) attaching the multilayer thin film type electrode to the other surface of the one surface of the metal catalyst layer in contact with the support layer; And

5) coating insulating portions on both sides of the silicon wafer or the remaining layer (2-5) except for the glass substrate (1) and the cathode (6);

.

When the solid oxide fuel cell according to the present invention is applied to a semiconductor manufacturing process, it can be applied to a semiconductor or a display with a fine structure. In spite of this fine structure, the efficiency of the solid oxide fuel cell is excellent. Also, since the multilayer thin film structure increases the ion conductivity and reduces the internal resistance of the battery, the output of the solid oxide fuel cell is increased. In addition, there is an effect of facilitating the large-scale mounting by preventing electrical short-circuiting due to defects during the large-area mounting. In addition, the multilayer thin film portion can be peeled off from Si by a lift-off process and adhered to another flexible material, thereby realizing a low-cost flexible fuel cell.

1 is a view showing the structure of a solid oxide fuel cell manufactured according to an embodiment of the present invention.
2 is a view showing the structure of a multilayer thin film electrode manufactured according to an embodiment of the present invention.
FIG. 3 is a graph showing the energy bands of particles moving within the 1-D Periodic Potential. FIG.
4 is a view showing a structure of a multilayer thin film electrode formed on a silicon wafer or a glass substrate and showing a metal catalyst layer deposited on a support layer on which a channel is formed.
5 is a view showing a spacer process used in a semiconductor process.
6 is a view showing a process of forming a support layer and a metal catalyst layer before stack deposition.
FIG. 7 is a view showing the manufacturing process of the embodiment according to the present invention in sequence.

Accordingly, the inventor of the present invention has made extensive efforts to develop a solid oxide fuel cell that has a fine structure and is excellent in efficiency and can be applied to a semiconductor or a display manufacturing process. As a result, the solid oxide fuel cell according to the present invention and its manufacturing method Thus completing the present invention.

Generally, YSZ (yttria stabilized zirconia), which is mainly used as an electrolyte in a high temperature type solid oxide fuel cell, has an ion conductivity of 0.005 S / cm, and it is difficult to obtain effective conductivity at low temperatures unless the thickness of the electrolyte is made ultra thin. In order to realize a low temperature type solid oxide fuel cell, thinning of electrolyte and electrode using semiconductor or display process is effective. Various structures have been proposed to integrate solid oxide fuel cells into a stack structure, but structures and materials applicable to existing semiconductor or display production processes have not yet been developed. In the present invention, a solid oxide fuel cell including a multilayer thin film electrode applicable to a conventional semiconductor or display production process and a manufacturing method thereof are proposed to increase the productivity and reduce the cost.

Specifically, the solid oxide fuel cell according to the present invention comprises

A silicon wafer or a glass substrate 1 having a top surface coated with a thin film of SiO or SiN is located at the bottom;

The support layer (2) is placed on the SiO or SiN thin film;

A metal catalyst layer 3 is attached and positioned on the other surface of the support layer in contact with the SiO 2 or SiN thin film;

A multilayer thin film electrode (4) is attached to the other surface of the metal catalyst layer, which is in contact with the support layer.

The upper surface of the silicon wafer or the glass substrate is coated with SiO 2 or SiN thin film to stably fix the support, thereby protecting the silicon wafer or the glass substrate from damage. Also, the SiO or SiN thin film is the same as the material of the support layer, and plays a role of connecting the silicon wafer or the glass substrate with the support layer.

The support layer is preferably formed on a SiO or SiN thin film. The support layer is not particularly limited, but preferably it is formed by photo / etch patterning using a channel-shaped mask. Further, the support layer is made of SiO or SiN, and is preferably composed of a plurality of supports. Further, although the shape of the support member is not particularly limited, it may preferably be a cylindrical shape or a square pillar. In addition, although the size of the support is not particularly limited, in the case of a cylindrical shape, its diameter may preferably be 10 nm to 10 μm. When the diameter of the cylindrical support is less than 10 nm, a sufficient support effect can not be achieved, which is undesirable. When the diameter of the support exceeds 10 탆, a fine and elaborate structure can not be achieved.

A metal catalyst layer is attached to the other surface of the support layer in contact with the SiO 2 or SiN thin film. At this time, the metal catalyst layer is not particularly limited, but Pd or Pt is preferable. The thickness of the metal catalyst layer is preferably 50-120 nm. When the thickness of the metal catalyst layer is more than 120 nm, the thickness of the metal catalyst layer becomes excessively thick and the entire microstructure is inhibited. So that it is not preferable. The metal catalyst layer is preferably formed by vapor deposition.

A multilayer thin film type electrode is formed on the other surface of the metal catalyst layer in contact with the support layer. In a general fuel cell, a separator is provided between the anode 5 and the cathode 6 to collect current and supply each fuel gas. Due to the separation plate formed with the flow path, various structures and additional processes are required to integrate the solid oxide fuel cell stack. However, since the solid oxide fuel cell according to the present invention has no separation plate between the multilayer thin film type electrodes, it can be manufactured with a fine and precise structure, and thus can be applied to a semiconductor or a display process. The multi-layer thin-film electrode has an anode electrode on one side and a cathode electrode on the other side of the electrode, and an electrolyte exists between the anode and the cathode. In addition, it is preferable that the multilayer thin film type electrode includes an electrolyte between a plurality of anode / cathode common electrodes. The anode / cathode common electrode is an electrode positioned between the anode and the cathode, and is referred to as an anode / cathode common electrode in the present invention. By controlling the thickness and physical properties of the multilayer thin film electrode, the current output of the fuel cell can be obtained at a desired voltage.

In the multilayer thin film type electrode according to the present invention, the thickness of the electrolyte and the electrode is described as a kinetic equation of a particle moving at a periodic potential quantitatively because the distance is sufficiently small compared to the diffusion length (~ 100 nm) of the ions passing through the electrolyte.

[1-D Kronich-Penny model in quantum mechanics]

<Formula 1>

The solution of Equation (1) is as follows.

<Formula 2>

를 찾는데

를

의 eigenstate

이라 하고

와

를 찾는다. 여기서

는 Lattice Vector,

는 Translation Operator 이며,

는 전도 이온에 대한 Hamiltonian 이다. 상기 운동방정식의 해는 Bloch function으로 잘 알려져 있는데 이는 에너지 밴드 내에서 움직이는 전자의 운동방정식과 유사하게 된다. 즉 고체 내에서 전자의 valence band와 conduction band사이에 forbidden band가 있듯이 수소/ 산소 이온이 전파될 수 있는 전압의 에너지 Band가 정해지게 된다.In the above formula

To find

To

Eigenstate

And

Wow

. here

Lattice Vector,

Is a translation operator,

Is the Hamiltonian for the conduction ion. The solution of the above equation of motion is well known as the Bloch function, which is similar to the equation of motion of electrons moving in the energy band. In other words, as there is a forbidden band between the valence band and the conduction band of the electrons in the solid, the energy band of the voltage at which the hydrogen / oxygen ion can propagate is determined.

Therefore, it is possible to obtain the fuel cell current output of the desired voltage by controlling the thickness and physical properties of the electrolyte / electrode of the multilayer thin film electrode.

The anode / cathode common electrode in the multilayer thin-film electrode is preferably formed by evaporation, and the evaporation method may preferably be ALD, PLD, CVD (including LP-CVD and PE-CVD).

In the case of a single layer corresponding to one cell in the multi-layer thin-film electrode, the thickness is preferably 1-100 nm although there is no particular limitation. Also, it is preferable that the thickness of the electrode and the electrolyte forming each single layer in the multilayer thin film electrode is 0.8-1.2: 0.8-1.2. In the deposition of the electrode to form the single layer, the deposition is not particularly limited, but it is preferable to perform 18-22 times. This repeats a single layer, preferably 18-22 layers. As a result, the total thickness of the multi-layer thin-film electrode may preferably correspond to 350 to 450 nm.

In addition, the multilayer thin film structure increases the ion conductivity, thereby reducing the internal resistance of the battery, thereby increasing the output of the solid oxide fuel cell. In addition, there is an effect of facilitating the large-scale mounting by preventing electrical short-circuiting due to defects during the large-area mounting.

Such a multilayer thin film electrode can be used to manufacture a flexible fuel cell when it is transferred to a bent metal substrate or a plastic substrate. At this time, there is no particular limitation, but it is preferable that the Si or the glass substrate is peeled off and bonded to another flexible material preferably by a lift-off process.

The material of the anode, the cathode and the anode / cathode common electrode is preferably at least one selected from the group consisting of platinum, palladium, ruthenium, vanadium, nickel, copper, gold, silver, tungsten, graphene and carbon nanotubes Do.

The electrolyte preferably comprises an oxygen ion conductive solid oxide or a hydrogen ion conductive solid oxide. The oxygen ion conductive solid oxide is at least one selected from the group consisting of zirconia, ceria and lanthanum gallate, and the hydrogen ion conductive solid oxide is at least one selected from the group consisting of barium zirconate, barium cerate, strontium zirconate , And the like.

Of the oxygen-ion conductive solid oxides, zirconia is preferably doped with yttrium or scandium. The ceria in the oxygen-ion conductive solid oxide is preferably doped with at least one selected from the group consisting of gadolinium, samarium, lanthanum, ytterbium, and neodymium. Also, the lanthanum gallate among the oxygen ion conductive solid oxides is preferably doped with strontium or magnesium.

It is also preferable that the hydrogen-ion conductive solid oxide is at least one selected from the group consisting of barium zirconate doped with a trivalent element, barium sulfate, strontium citrate and strontium zirconate.

Both sides of the solid oxide fuel cell according to the present invention preferably comprise an insulating portion 7 including SiO or SiN.

The solid oxide fuel cell according to the present invention has a fine structure and can be applied to a semiconductor or a display manufacturing process, and has excellent efficiency as a solid oxide fuel cell.

A method of manufacturing a solid oxide fuel cell according to another aspect of the present invention includes:

1) depositing a thin film of SiO or SiN on top of a silicon wafer or glass substrate;

2) forming a support layer on the deposited SiO or SiN thin film;

3) depositing a metal catalyst layer on the other surface of the surface of the support layer where the SiO 2 or SiN thin film is in contact with the support layer;

4) attaching the multilayer thin film type electrode to the other surface of the one surface of the metal catalyst layer in contact with the support layer; And

5) coating insulating portions on both sides of the silicon wafer or the remaining layer (2-5) except for the glass substrate (1) and the cathode (6);

.

In the method of manufacturing a solid oxide fuel cell according to the present invention, the deposition method may preferably be ALD, PLD, CVD (including LP-CVD and PE-CVD), and the deposition temperature is preferably 500-1,000 ° C Do.

By the above step 1), the SiO 2 or SiN thin film is coated on the silicon wafer or the glass substrate to stably fix the support, thereby protecting the silicon wafer or the glass substrate from damage. Also, the SiO or SiN thin film is the same as the material of the support layer, and plays a role of connecting the silicon wafer or the glass substrate with the support layer.

There is no particular limitation on the method of forming the supporting layer by the step 2), but it is preferable to form it by Photo / Etch patterning using a flow-path mask. Further, the support layer is made of SiO or SiN, and is preferably composed of a plurality of supports. Further, although the shape of the support member is not particularly limited, it may preferably be a cylindrical shape or a square pillar.

It is preferable that the planarization process is performed by a CMP process before the metal layer is deposited after the support layer is formed.

The material of the metal catalyst layer deposited by the step 3) preferably includes Pd or Pt.

In the multi-layer thin film electrode deposited by the step 4), an anode electrode is formed on one side of the electrode, and a cathode electrode is formed on the other side of the electrode. Electrolyte is present between the anode and the cathode. In addition, it is preferable that the multilayer thin film type electrode includes an electrolyte between a plurality of anode / cathode common electrodes. The anode / cathode common electrode is an electrode positioned between the anode and the cathode, and is referred to as an anode / cathode common electrode in the present invention. By controlling the thickness and physical properties of the multilayer thin film electrode, the current output of the fuel cell can be obtained at a desired voltage. After depositing the multilayer thin film electrode, the remaining portion is etched while leaving only the cell area of the desired stack portion.

Both sides of the silicon wafer or the remaining layer 2-5 except for the glass substrate 1 and the cathode 6 among the solid oxide fuel cells manufactured by the steps 1) to 4) are connected to the insulating portion Coating. These 5) steps are capped by an insulator such as SiN using a Spacer process to prevent ions or fuel from leaking.

Finally, the cathode electrode is deposited by the above step 6, and then patterned to open the oxygen supply part, and a wire is connected to the contact pad to be packaged in a semiconductor chip.

Thus, the solid oxide fuel cell manufactured by the method of the present invention can be applied to a semiconductor or a display manufacturing process, and has excellent efficiency as a solid oxide fuel cell.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Example

SiO or SiN is deposited on a silicon wafer by LPCVD at 500 ℃ to form a thin film, and then a supporting layer is formed by photo / etch patterning using a flow mask. After depositing a thin metal catalyst layer (Pd) on the support layer within 100 nm, the multilayer thin film electrode is deposited.

At this time, SiO or SiN is used because the support layer can have various line pattern (Line & Space: L / S) such as serpentine or square array / circular array pattern and corrosion resistance.

In addition, when the electrode metal catalyst layer (Pd or Pt) is deposited on the support layer pattern, the metal catalyst layer is not formed properly due to the step difference. Therefore, SiO is deposited on the support layer and then planarized by CMP (Chemical Mechanical Polish) process. After depositing a metal catalyst layer (Pd), an oxide etchant (eg LAR etch: a low ammonium fluoride liquid (LAL) chemical ~ etch rate: 20 nm / min, HF 0.7%, NH 4 F 17%, H ₂ O, , Techno Semichem Co., Ltd.), the SiO 2 between the support layer and the metal catalyst layer is removed and a hollow structure is formed, thereby enabling a smooth supply of hydrogen fuel.

As another method of forming the supporting layer, it is also possible to deposit a sublimable material (for example, As) instead of SiO 2 between the supporting layer and the metal catalyst layer, planarize the CMP process, and then deposit the metal catalyst layer. When the temperature is raised above the sublimation temperature (615 ° C), As filled in the support layer and the metal catalyst layer is vaporized and a hollow structure is formed, so that a sufficient supply of hydrogen fuel is possible.

After depositing the multilayer thin-film electrode, the remaining portion is etched by leaving the desired cell area of the stack portion, and then the side of the multilayer thin-film electrode and the supporting layer is capped by a SiN insulator using a spacer process so that ions or fuel do not leak. Finally, after cathodic electrode was deposited, patterning was performed to open the part to which oxygen was supplied, and a wire was connected to the contact pad to be packaged in a chip.

At this time, the deposition of the multilayer thin film electrode was repeated 20 times by depositing the anode electrode on the metal catalyst layer, filling the electrolyte, and then depositing the anode / cathode common electrode again. Thickness ratios of electrolyte and electrode were 1: 1 and twenty times were repeated to fabricate 20 layer multilayer thin film electrodes. At this time, one electrolyte was 10 nm thick and one electrode was 10 nm thick. The total thickness of the stack was 20 nm and the thickness was 400 nm. Here, YSZ was used as an electrolyte, and Pd was used as a metal catalyst layer, an anode / cathode common electrode, an anode electrode, and a cathode electrode.

The solid oxide fuel cell fabricated according to the present embodiment is shown in FIG. 1, and the structure of the multilayer thin film electrode is shown in FIG. In FIG. 2, the electrode in the multilayer thin film except for the external electrode to which hydrogen / oxygen gas fuel is supplied constitutes an anode / cathode common electrode, and hydrogen ions or oxygen ions pass through the electrolyte without reacting. FIG. 3 also shows a graph showing the energy band of moving particles in the 1-D periodic potential (Bloch Theorem describing the electrolyte / electrode multilayer thin film structure as periodic potential, left: Discontinuous energy level, right: energy band spectrum of moving particles at 1-D periodic potential). 4 shows a structure (left) of a multilayer thin film electrode formed on a silicon wafer or a glass substrate and is a diagram (right) showing a metal catalyst layer deposited on a support layer on which a flow path is formed. 5 is a view showing a Spacer process (using SiO or SiN as a capping layer) used in a semiconductor process. 6 is a view showing a process of forming a support layer and a metal catalyst layer before deposition of a multilayer thin film electrode. 7 is a diagram sequentially showing the manufacturing process of this embodiment.

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, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. It is natural.

1. Silicon wafer or glass substrate
2. Support layer
3. Metal catalyst layer
4. Multilayer thin film electrode
5. Anode
6. Cathode
7. Insulation

Claims (14)

A silicon wafer or a glass substrate coated with a thin film of SiO or SiN on its upper surface is located at the bottom;
A support layer is disposed on the SiO or SiN thin film;
A metal catalyst layer is adhered and disposed on the other surface of the support layer in contact with the SiO 2 or SiN thin film;
And a multilayer thin film type electrode is attached to the other surface of the one side of the metal catalyst layer in contact with the support layer.
The method according to claim 1,
Wherein the support layer is made of SiO or SiN, and is composed of a plurality of supports.
The method according to claim 1,
Wherein the metal catalyst layer comprises Pd or Pt.
The method according to claim 1,
The multilayer thin film type electrode includes an anode and a cathode on both sides thereof, and an electrolyte between the anode and the cathode. The multilayer thin film type electrode includes an electrolyte between a plurality of anode / cathode common electrodes Characterized by a solid oxide fuel cell.
5. The method of claim 4,
The material of the anode, the cathode and the anode / cathode common electrode is at least one selected from the group consisting of platinum, palladium, ruthenium, vanadium, nickel, copper, gold, silver, tungsten, graphene and carbon nanotubes Wherein the solid oxide fuel cell is a solid oxide fuel cell.
5. The method of claim 4,
Wherein the electrolyte comprises an oxygen ion conductive solid oxide or a hydrogen ion conductive solid oxide,
Wherein the oxygen ion conductive solid oxide is at least one selected from the group consisting of zirconia, ceria and lanthanum gallate,
Wherein the proton conductive solid oxide is at least one selected from the group consisting of barium zirconate, barium cerate, strontium cerate, and a perovskite group of strontium zirconate.
delete 1) depositing and coating a thin film of SiO or SiN on a silicon wafer or a glass substrate;
2) forming a support layer on the deposited SiO or SiN thin film;
3) depositing a metal catalyst layer on the other surface of the surface of the support layer where the SiO 2 or SiN thin film is in contact with the support layer;
4) attaching the multilayer thin film type electrode to the other surface of the one surface of the metal catalyst layer in contact with the support layer; And
5) coating insulating portions on both sides of the supporting layer and the multilayer thin film type electrode;
Wherein the solid oxide fuel cell comprises a solid oxide fuel cell.
9. The method of claim 8,
Wherein the support layer is made of SiO or SiN, and is formed of a plurality of supports.
9. The method of claim 8,
Wherein the metal catalyst layer comprises Pd or Pt.
9. The method of claim 8,
The multilayer thin film type electrode includes an anode and a cathode on both sides thereof, an electrolyte between the anode and the cathode, and an electrolyte between the anode and the cathode common electrode in the multilayer thin film type electrode Wherein the solid oxide fuel cell comprises a solid oxide fuel cell.
12. The method of claim 11,
The material of the anode, the cathode and the anode / cathode common electrode is at least one selected from the group consisting of platinum, palladium, ruthenium, vanadium, nickel, copper, gold, silver, tungsten, graphene and carbon nanotubes Of the solid oxide fuel cell.
12. The method of claim 11,
Wherein the electrolyte comprises an oxygen ion conductive solid oxide or a hydrogen ion conductive solid oxide,
Wherein the oxygen ion conductive solid oxide is at least one selected from the group consisting of zirconia, ceria and lanthanum gallate,
Wherein the hydrogen-ion conductive solid oxide is at least one selected from the group consisting of barium zirconate, barium sulfate, strontium sulfate and strontium zirconate.
9. The method of claim 8,
Wherein the flattening process is performed by a CMP process before the metal catalyst layer is deposited after the support layer is formed.

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