KR20230119471A - Deposition apparatus using plasma - Google Patents

Abstract

The present invention is a deposition apparatus using plasma, which includes an electrode 11, N _{2 ,} Ar, H ₂ gas supply port 12, gas distribution (dispersion filter) 13, active region 15, nozzle 14 , a platinum-based metal-containing compound solution supply port 31, a conductive material-dispersed solution or an insulating material-dispersed solution supply port 32, N ₂ and H ₂ carrier gas supply port 41. It is a deposition apparatus composed of a platinum-based metal-containing compound solution, a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed, a mixing chamber 21 in which a carrier gas is mixed, and a mixed solution and a carrier gas supply port 51.

Description

Deposition apparatus using plasma {DEPOSITION APPARATUS USING PLASMA}

The present invention relates to a deposition apparatus using plasma, and specifically, to a deposition apparatus capable of simultaneously depositing a platinum-based metal and a conductor or a platinum-based metal and an insulator.

Fossil fuels, such as petroleum, coal, and natural gas, account for more than 80% of current energy demand. However, at current rates of depletion, reserves will be depleted within 50 years. In addition, fossil fuels pose a threat to human survival by causing environmental problems such as global warming, ozone layer destruction, dust dome, and acid rain due to various pollutants generated during combustion. In order to wisely overcome such a crisis, it is very necessary to develop clean and safe alternative energy that is not depleted. In this context, hydrogen energy is attracting the most attention as an ideal alternative energy for the next generation.

Hydrogen can be produced by decomposing water, and is also captured as a by-product in chemical processes. When hydrogen reacts with oxygen, energy is obtained and then recycled into water, which is environmentally friendly. In addition, since hydrogen energy is easily converted into other forms of energy such as heat and electricity, it can be applied to secondary batteries and heat pumps. When hydrogen is used as a fuel, its heat per unit weight is more than three times that of gasoline or natural gas. high, and the burning rate is more than 10 times greater. Furthermore, since water is an infinite resource, the acquisition of hydrogen energy technology obtained from water has the characteristic of securing energy resources.

Current hydrogen energy-related technologies include water splitting electrolyzers and fuel cells.

A water decomposition electrolytic cell means an electrochemical cell that converts electrical energy into chemical energy, and represents an electrochemical cell that mainly generates hydrogen by electrolyzing water. Since pure water is difficult to electrolyze, it is generally decomposed by adding SO ₂ gas to water to obtain hydrogen gas and sulfuric acid (H ₂ SO ₄ ) as products. Examples of the water electrolysis method include alkaline water electrolysis, polymer electrolyte membrane water electrolysis, and high-temperature steam water electrolysis.

On the other hand, a fuel cell means an electrochemical cell that converts chemical energy generated by oxidation of fuel into electrical energy. Unlike a chemical cell in which reactants are continuously supplied from the outside, and reaction products are continuously discharged to the outside of the system. The fuel cell is classified according to the operating temperature and electrolyte, and these are a molten carbonate electrolyte fuel cell (MCFC) operated at high temperature (about 500 ~ 700 ℃), a phosphoric acid electrolyte fuel cell (PAFC) operated near 200 ℃, room temperature Alkaline fuel cells (AFCs), polymer electrolyte fuel cells (PEMFCs), or direct methanol fuel cells (DMFCs) operating at temperatures of up to about 100° C. are typical.

Among these electrochemical cells, in particular, electrochemical cells using polymer membranes are thin (mainly 1 mm or less) and light, and have excellent electricity generating ability, so they can be applied to various fields, but have the disadvantage of using expensive platinum-based catalysts Therefore, the effectiveness of the platinum catalyst is increased and the manufacture of a catalyst layer made through an economical process has been a major challenge. In addition to the development of an economical electrode catalyst manufacturing method, in the case of a water decomposition electrolytic cell or a direct methanol fuel cell using the water/SO ₂ mixture as a reaction gas, SO ₂ molecules or methanol as a fuel are reduced from the oxidizing electrode through the polymer electrolyte There is a problem in that the performance of the electrochemical cell deteriorates as it is passed through the electrode. As a way to solve this problem, there is a method of depositing a palladium (Pd) film on the surface of a solid polymer electrolyte, but economical deposition of this material also remains an important problem.

The electrode of the electrochemical cell using the solid polymer film as an electrolyte is a platinum group element such as platinum (Pt), ruthenium (Ru), palladium (Pd), osmium (Os), iridium (Ir), rhodium (Rh), gold ( It is composed of Au), silver (Ag), iron (Fe), nickel (Ni), molybdenum (Mo) or an alloy between them. These materials are expensive precious metal materials, and should be designed to achieve maximum energy conversion in a small amount because of economic feasibility when used as an electrode catalyst. Here, in order to increase the current value per material amount, the surface area of the electrode must be maximized. To this end, the noble metal material must be made into small particles if possible and deposited on an electrode support or an electrolyte to increase the usability of the electrode catalyst.

Two methods are mainly used for depositing the platinum-based catalyst layer. First, in order to increase the utilization of the platinum catalyst, nano-sized particle powder or carbon particles in which nano-sized platinum particles are dispersed and adsorbed are mixed with a solution containing a hydrogen ion conductive polymer material (eg, Nafion ionomer of DuPont). This is a method of preparing a catalyst ink by mixing and depositing it on an electrode support or an electrolyte. In the case of such a catalyst deposition method, there is a disadvantage in that an expensive commercial platinum-based catalyst is used because pre-prepared catalyst powder is used. Specifically, compounds containing these elements are used as precursors to obtain platinum-based particle powder. For example, in the case of platinum, a solution is prepared by dissolving a salt compound such as hydrogen hexachloro platinum (IV) hydrate (H ₂ PtCl ₆ ) or platinum (II) chloride (PtCl ₂ ) in a solvent as a precursor. At this time, water, alcohol, acid, base, or organic solvent is used as the solvent. A reducing agent such as lithium borohydride (LiBH4) or sodium borohydride (NaBH4) is added to the solution prepared as described above to reduce the precursor to make the platinum-based metal contained therein into particles. In particular, when metal particles are formed in a solution by a reduction reaction, in order to make them small in nano size, a stabilizer is added to the surface of the growing particles to prevent them from increasing to a certain size or more. As the stabilizer, polyvinyl-pyrrolidone (PVP) or the like is used. As described above, a solution containing various chemicals is usually heated and stirred for 10 to 24 hours to obtain nano metal particles having a stabilizer adsorbed on the surface. At this time, when the carbon powder is put into the solution, the generated metal particles are dispersed and adsorbed on the surface of the carbon particles (support). After the prepared metal particles are separated from the solution, the stabilizer is removed from the metal surface by a method such as heating to obtain a material in a final form that can be used as an electrocatalyst.

As described above, the method of depositing a catalyst layer using the previously prepared catalyst powder has a disadvantage in that the price of catalyst particles increases because a very complicated process and time are invested in preparing the catalyst.

In the conventional catalyst layer deposition method, the method using a pre-prepared catalyst takes a considerably long time to prepare the catalyst, 10 to 24 hours, and has a problem that the chemical treatment process is complicated due to the addition of a reducing agent and a stabilizer. In addition, in the method of depositing a catalyst layer using a vacuum vapor deposition method, a continuous process is difficult, takes a long deposition time, and commercialization is difficult due to expensive vacuum equipment.

Patent Document 1 discloses a "platinum-based metal thin film manufacturing apparatus for an electrode catalyst using plasma discharge", and the present invention includes a mixed gas injection unit for injecting a mixed gas of hydrogen gas and an inert gas; A first electrode having an insulator surrounding the surface of the electrode and having a substrate coated with a platinum-based metal-containing compound thin film on the insulator; A plasma reactor having a pair of electrode parts including a platinum-based metal-containing compound thin film applied on a substrate and a second electrode spaced apart at a predetermined interval (d); and a power supply unit connected to the first electrode and the second electrode of the electrode unit located inside the reactor to supply power to generate a plasma discharge. .

The manufacturing apparatus of Patent Document 1 needs to maintain a plasma reactor in a vacuum, and first, a platinum-based metal-containing compound solution is applied to a polymer electrolyte membrane or an electrode support layer substrate surface and dried to prepare a thin film made of a platinum-based metal-containing compound. After that, it is put in a plasma device and plasma is generated while supplying reducing gas to produce a platinum-based metal thin film. In order to increase the thickness of the deposited film, the same process must be repeated. There was a disadvantage that a vacuum facility was required.

Republic of Korea Patent No. 10-0792152

The conventional deposition apparatus for a platinum-based metal thin film using plasma discharge has disadvantages such as difficult continuous process, long deposition time, and expensive vacuum equipment. It is to provide a deposition apparatus for simultaneously and continuously depositing a platinum-based metal and an insulator.

The present invention is a deposition apparatus using plasma, wherein an electrode 11, N _{2 ,} Ar, H ₂ gas supply port 12, a gas distribution (dispersion filter) 13, and a platinum system activated in an active region 15 A nozzle 14 for injecting a metal-containing compound, a conductive material, and a carrier gas of N ₂ and H ₂ onto a substrate or a platinum-based metal-containing compound, an insulating material, and a carrier gas of N ₂ and H ₂ onto the substrate, platinum A supply port 31 of a solution containing a metal-based compound, a supply port 32 of a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed, and a carrier gas supply port 41 of N ₂ and H ₂ . A mixing chamber 21 in which a solution of a platinum-based metal-containing compound, a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed, and a carrier gas are mixed, a platinum-based metal-containing compound solution mixed in the mixing chamber, and a conductive material are dispersed It is characterized in that it consists of a solution or a solution in which an insulating material is dispersed, a mixed solution for supplying a carrier gas to the active region, and a carrier gas supply port 51.

The platinum-based metal-containing compound includes platinum (Pt), palladium (Pd), ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), gold (Au), silver (Ag), It is any one or an alloy component thereof selected from the group consisting of iron (Fe), nickel (Ni), and molybdenum (Mo), and the solution is characterized in that water.

The platinum-based metal-containing compound is a platinum-based metal compound combined with chlorine (Cl).

The conductive material is at least one of carbon (C) and carbon nanotube (CNT), and is characterized in that it is dissolved in water using an acidic dispersant.

The insulating material is a single metal oxide or a composite oxide of one of silicon dioxide (SiO ₂ ), aluminum oxide (Al 2 O ₃ ), zirconium dioxide (ZrO ₂ ), and hafnium dioxide (HfO ₂ ), and is dissolved in water using an acidic dispersant. characterized by

A supply pressure range of the N _{2 ,} Ar, H ₂ gas supplied to the plasma device is 5 to 10 Bar.

The gas distributor (dispersion filter) disperses the plasma throughout the active region.

A solution in which the platinum-based metal-containing compound solution and the conductive material are dispersed or a solution in which the platinum-based metal-containing compound solution and the insulating material are dispersed are mixed with a carrier gas of N ₂ and H ₂ in a mixing chamber and then supplied to the active region.

The ratio of the carrier gas N _{2 :} H ₂ is 80 to 95: 5 to 20, and the supply pressure is 2 to 4 Bar.

The supply pressure of the carrier gas is lower than that of the N _{2 ,} Ar, and H ₂ gases.

H ₂ in a solution in which a platinum-based metal-containing compound solution and a conductive material are dispersed, or in a solution in which a platinum-based metal-containing compound solution and an insulating material are dispersed, and a carrier gas supplied to the active region is activated by plasma to obtain reaction formula 1 to reaction formula The reaction is the same as in 4.

H ₂ MCl ₆ → M + 2HCl + 2Cl ₂ (Scheme 1)

H ₂ MCl ₆ + xH ₂ → M + 6HCl + (x-3)H ₂ (Scheme 2)

MCl ₆ + yH ₂ → M + 2HCl + 2Cl ₂ + (y-1)H ₂ (Scheme 3)

MCl ₆ + xH ₂ → M + 6HCl + (x-3)H ₂ (Scheme 4)

Power supplied to the plasma device is one of direct current, alternating current, and microwave power.

The frequency of the AC power supply is 50 Hz to 500 MHz, and the frequency of the microwave power supply is 1 to 10 GHz.

The voltage of the AC power supply is 0.1 to 50 kV, the current is 0.01 to 900 mA, and the power supplied by the voltage and current is 1 to 500 W per 1 cm2 of treatment area.

The thin film deposited with platinum-based metal is used in water decomposition electrolyzers, polymer electrolyte fuel cell electrodes, polymer electrolyte membranes coated with electrode catalyst layers, water/SO ₂ mixture electrolysis cells to produce hydrogen, and polymers constituting methanol fuel cells. It is characterized in that it is used as a permeation inhibition layer of SO ₂ or fuel on the surface of the electrolyte.

The deposition apparatus using the plasma of the present invention simultaneously and continuously deposits a platinum-based metal and a conductor, or a platinum-based metal and an insulator, but it is possible to deposit in a short time and does not require expensive vacuum equipment.

1 is a perspective view of a deposition process state using a deposition apparatus using a plasma of the present invention;
2 is a deposition apparatus using the plasma of the present invention,
3 is a photograph in which platinum (Pt) as a catalyst and carbon (C) as a conductive material are deposited on a substrate using the deposition method of the present invention.

Hereinafter, a deposition apparatus using plasma according to the present invention will be described in detail based on the accompanying drawings. For reference, the size of components, the thickness of lines, etc. shown in the drawings referred to in describing the present invention may be somewhat exaggerated for convenience of understanding.

In addition, the terms used in the description of the present invention are defined in consideration of the functions in the present invention, and may vary depending on the user, operator's intention, convention, and the like. Therefore, the definition of this term deserves to be made based on the contents throughout this specification.

And in this application, terms such as 'include' and 'have' refer to the existence of a specific number, step, operation, component, part, or combination thereof described in the specification, but one or more other It should be understood that the presence or addition of features, numbers, steps, operations, components, parts, or combinations thereof is not precluded.

In addition, the present invention is not limited to the embodiments disclosed below, but will be implemented in a variety of different forms, and only this embodiment makes the disclosure of the present invention complete, and the scope of the invention to those skilled in the art. It is provided for complete information.

Therefore, since the present invention can have various changes and various forms, implementation examples (態樣, aspects) (or embodiments) will be described in detail in the specification. However, this is not intended to limit the present invention to a specific disclosed form, and it should be understood to include all changes, equivalents, and substitutes included in the technical spirit of the present invention, and the singular expression used in this specification is clearly different from the context. Include plural expressions unless otherwise indicated.

However, in describing the present invention, detailed descriptions of known or known functions or configurations will be omitted to clarify the gist of the present invention.

Hereinafter, "upward", "downward", "front" and "rearward" and other directional terms are defined based on the state shown in the drawings.

The state of matter can be divided into solid, liquid, and gas. When energy is applied to a substance in a gaseous state, electrons are separated from atoms or molecules, resulting in a plasma state in which electrons and ions exist. From a macroscopic point of view, the plasma is electrically neutral, contains free charged holes and is electrically conductive. Plasma is a chemically reactive medium.

Normal pressure plasma of the present invention is generated by electric energy. The electric field is generated by electrons in the gas. An electric field transfers energy to electrons in a gas to become charged species, and energy is transferred to neutral species by collision.

A process of generating plasma using a simple plasma generating device will be described below. First, two flat conductors are separated by a certain distance d, and then a DC voltage V is applied to the conductors. In this case, a constant electric field is generated between the two conductors. At this time, the generated electric field E is generated under the condition that E=V/d, which is proportional to the voltage and inversely proportional to the distance. At this time, when the strength of the voltage exceeds a certain level, a small number of electrons start to be generated on the conductor plate to which the cathode is connected, and as these electrons move to the anode along the electrode, they collide with the gases existing between the two conductors, resulting in As the gases ionize, a discharge occurs. This process is called discharge initiation by avalanche. At this time, the ions move to the cathode along the electric field and hit the conductor plate connected to the cathode strongly, causing electrons to jump out of the cathode and accelerate the generation of plasma. This process is called secondary emission.

1 is a perspective view of a deposition process state using a deposition apparatus using a plasma of the present invention, Figure 2 is a deposition apparatus using a plasma of the present invention, and Figure 3 is a platinum (Pt) catalyst using the deposition method of the present invention This is a picture of carbon (C), a conductive material, deposited on a substrate.

Hereinafter, the deposition apparatus shown in FIGS. 1 and 2 will be described.

The deposition apparatus using the plasma shown in FIG. 2 is configured as follows.

Referring to FIG. 2, the plasma device 10 includes an electrode 11, N _{2 ,} Ar, H ₂ gas supply port 12, a gas distributor (dispersion filter) 13, an activated platinum-based metal-containing compound and It consists of a nozzle 14 for injecting a conductive material and a carrier gas of N ₂ and H ₂ to the substrate or injecting a platinum-based metal-containing compound and an insulating material and a carrier gas of N ₂ and H ₂ to the substrate, and A supply port 31 of a solution containing a metal-based compound, a supply port 32 of a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed, and a carrier gas supply port 41 of N ₂ and H ₂ . A mixing chamber 21 in which a solution of a platinum-based metal-containing compound, a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed, and a carrier gas are mixed, a platinum-based metal-containing compound solution mixed in the mixing chamber, and a conductive material are dispersed A solution or a solution in which an insulating material is dispersed, a mixed solution for supplying a carrier gas to the active region, and a carrier gas supply port 51.

The activated platinum-based metal-containing compound and the conductive material, or the platinum-based metal-containing compound and the insulating material, and the carrier gas of N ₂ and H ₂ sprayed from the nozzle 14 are sprayed onto the substrate 100 to form a platinum-based metal and conductive material. A material or platinum-based metal and an insulating material are deposited.

Looking at the operation process of the present invention, first, N _{2 ,} Ar, H ₂ gas of N 2 and Ar gas is supplied from a N _{2 ,} Ar _, H ₂ gas storage container (not supplied) to the plasma device 10, N _{2 ,} Ar, Plasma is generated and supplied to the active region 15 while being supplied to the H ₂ gas supply port 12 .

The supply pressure of the N _{2 ,} Ar, H ₂ gas is 5 to 10 bar, preferably 5 to 8 bar.

At this time, it is preferable to pass the generated plasma through a gas distributor (dispersion filter) 13 capable of dispersing droplets by a pressure difference to disperse the plasma and supply it to the active region 15, and the gas distributor (dispersion filter) (13) is for dispersing the concentration of plasma generated in the plasma device.

Next, a solution in which a platinum-based metal-containing compound solution and a conductive material are dispersed, or a solution in which a platinum-based metal-containing compound solution and an insulating material are dispersed are mixed with a carrier gas of N ₂ and H ₂ in the mixing chamber 21 to obtain platinum A solution in which a metal-containing compound solution and a conductive material are dispersed is supplied to the active region together with a carrier gas of _{N 2} and H ₂ , or a solution in _which a platinum-based metal-containing compound solution and an insulating material are dispersed is supplied to the active region. It is supplied to the active region 15 together with the carrier gas.

The ratio of N _{2 :} H ₂ , which is the carrier gas supplied to the mixing chamber 21, is 80 to 95: 5 to 20, and the supply pressure is 2 to 4 Bar.

The supply pressure of the N _{2 ,} Ar, and H ₂ gases must be higher than the supply pressure of the carrier gas supplied to the mixing chamber 21 . When the N _{2 ,} Ar, H ₂ gas supplied at high pressure moves while leading the generated plasma to the active area 15, it passes through the gas distributor (dispersion filter) 13 to disperse the plasma to form the active area 15. and serves to disperse droplets of a platinum-based metal-containing compound solution supplied from the mixing chamber to the active area 15 at a relatively low pressure and a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed. do.

A solution in which a platinum-based metal-containing compound solution and a conductive material are dispersed, or a solution in which a platinum-based metal-containing compound solution and an insulating material are dispersed, supplied to the active region 15 are vaporized and activated by plasma.

Since plasma accompanies heat, a solution in which a platinum-based metal-containing compound solution and a conductive material are dispersed or a solution in which a platinum-based metal-containing compound solution and an insulating material are supplied to the active region 15 are vaporized and activated.

At this time, a reduction reaction in which the platinum-based metal-containing compound is decomposed into platinum-based metal, hydrogen, and chlorine is activated.

The activated platinum-based metal-containing compound and a conductive material, or a platinum-based metal-containing compound and an insulating material, and a carrier gas of N ₂ and H ₂ are sprayed onto the substrate. At this time, heating the substrate at 700 to 800° C. is effective in depositing the reduced platinum-based metal (M), conductive material, and insulating material on the substrate.

H ₂ in a solution in which a platinum-based metal-containing compound solution and a conductive material are dispersed, or in a solution in which a platinum-based metal-containing compound solution and an insulating material are dispersed, and a carrier gas supplied to the active region is activated by plasma to obtain reaction formula 1 to reaction formula The reaction is the same as in 4.

H ₂ MCl ₆ → M + 2HCl + 2Cl ₂ (Scheme 1)

H ₂ MCl ₆ + xH ₂ → M + 6HCl + (x-3)H ₂ (Scheme 2)

MCl ₆ + yH ₂ → M + 2HCl + 2Cl ₂ + (y-1)H ₂ (Scheme 3)

MCl ₆ + xH ₂ → M + 6HCl + (x-3)H ₂ (Scheme 4)

The platinum-based metal (M)-containing compound includes platinum (Pt), palladium (Pd), ruthenium (Ru), osmium (Os), rhodium (Rh), iridium (Ir), gold (Au), silver ( Ag), iron (Fe), any one selected from the group consisting of nickel (Ni) and molybdenum (Mo) or an alloy component thereof, and the solution is water.

The platinum-based metal (M)-containing compound is a platinum-based metal compound combined with chlorine (Cl).

The conductive material is at least one of carbon (C) and carbon nanotube (CNT), and dissolves in water using an acidic dispersant.

The insulating material is a single metal oxide or a composite oxide of one of silicon dioxide (SiO ₂ ), aluminum oxide (Al 2 O ₃ ), zirconium dioxide (ZrO ₂ ), and hafnium dioxide (HfO ₂ ), and is dissolved in water using an acidic dispersant. .

Power supplied to the plasma device is one of direct current, alternating current, and microwave power.

The frequency of the AC power supply is 50 Hz to 500 MHz, and the frequency of the microwave power supply is 1 to 10 GHz.

The voltage of the AC power supply is 0.1 to 50 kV, the current is 0.01 to 900 mA, and the power supplied by the voltage and current is 1 to 500 W per 1 cm2 of treatment area.

The thin film deposited with the platinum-based metal according to the present invention is a water decomposition electrolytic cell, an electrode of a polymer electrolyte fuel cell, a polymer electrolyte membrane coated with an electrode catalyst layer, a water/SO ₂ mixture electrolysis tank for producing hydrogen, and a methanol fuel cell. It is used as a permeation suppression layer of SO ₂ or fuel on the surface of the polymer electrolyte constituting the.

<Example> Preparation of platinum and carbon layer

H ₂ PtCl ₆ was dissolved in water to prepare a platinum-containing compound solution having a concentration of 10% by weight. A solution in which carbon nanotubes are dispersed in water by an acidic dispersant is prepared.

While supplying N _{2 ,} Ar, and H ₂ gases to the plasma device at a pressure of 6 Bar, plasma was generated and passed through a gas distributor to supply plasma and inert gas to the active region 15 . A solution obtained by dispersing carbon nanotubes in the previously prepared platinum-containing compound solution and water by acid dispersing agent, and a carrier gas are supplied to the mixing chamber 21, respectively, and carbon nanotubes are dispersed in the platinum-containing compound solution and water by acid dispersing agent. While mixing the solution and the carrier gas, the mixed gas was supplied to the active region.

In the active area, H ₂ PtCl ₆ → Pt + 2HCl + 2Cl ₂ reaction occurs and is activated, and carbon (C) of the carbon nanotube is also activated.

Activated platinum (Pt) and carbon (C) were sprayed onto the heated substrate to deposit platinum (Pt) and carbon (C) on the substrate. X-ray diffraction analysis (X-ray diffraction) of platinum (Pt) and carbon (C) components reduced from the plasma device or reduced from the substrate and deposited on the substrate using an X-ray diffractometer (Rigaku-SA-HF3) Diffraction: XRD) was performed, and the results are shown in FIG. 3 .

As shown in FIG. 3, it was confirmed that the platinum and carbon thin films deposited on the substrate were composed of pure platinum (Pt) without chlorine (Cl). Therefore, the conductive layer of platinum (Pt) and carbon (C) prepared according to the present invention is a pure platinum thin film and can be used as an electrode catalyst layer of an electrochemical cell.

Although the invention made by the present inventors has been specifically described according to the above embodiments, the present invention is not limited to the above embodiments and can be changed in various ways without departing from the gist of the invention.

Plasma device (10)
Electrode (11) N _2, Ar, H ₂ Gas supply port (12)
Gas distributor (dispersion filter) (13) Nozzle (14)
Activation area (15)
Mixing chamber (21)
Supply port 31 of a platinum-based metal-containing compound solution
Supply port 32 of a solution in which a conductive material is dispersed or an insulating material is dispersed in a solution
Carrier gas supply port (41) Mixed solution and carrier gas supply port (51)
Substrate(100)

Claims (4)

electrode 11;
N _2, Ar, H ₂ gas supply port (12),
Gas distribution (dispersion filter) (13),
Active area (15),
nozzle 14;
A supply port 31 for a platinum-based metal-containing compound solution;
A supply port 32 of a solution in which a conductive material is dispersed or a solution in which an insulating material is dispersed,
N ₂ and H ₂ carrier gas supply port (41).
A mixing chamber 21 in which a platinum-based metal-containing compound solution, a conductive material-dispersed solution or an insulating material-dispersed solution, and a carrier gas are mixed;
A deposition apparatus using plasma, characterized in that it consists of a mixed solution and a carrier gas supply port (51). According to claim 1,
The mixed solution and carrier gas supply port 51 supplies the platinum-based metal-containing compound solution mixed in the mixing chamber, the conductive material-dispersed solution or the insulating material-dispersed solution, and the carrier gas to the active region 15. Evaporation apparatus using the characterized plasma. According to claim 1,
The active region 15 is a solution in which a platinum-based metal-containing compound solution and a conductive material are dispersed, or a solution in which a platinum-based metal-containing compound solution and an insulating material are dispersed, and H ₂ in a carrier gas is activated by plasma. Evaporation device using plasma According to claim 1,
The ratio of the carrier gas N _{2 :} H ₂ is 80 to 95 : 5 to 20, and the supply pressure of the carrier gas is lower than the pressure of the N _{2 ,} Ar, H ₂ gas.

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