WO2018101665A1 - Method for manufacturing semiconductor coating film by using magnetization - Google Patents

Method for manufacturing semiconductor coating film by using magnetization Download PDF

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WO2018101665A1
WO2018101665A1 PCT/KR2017/013201 KR2017013201W WO2018101665A1 WO 2018101665 A1 WO2018101665 A1 WO 2018101665A1 KR 2017013201 W KR2017013201 W KR 2017013201W WO 2018101665 A1 WO2018101665 A1 WO 2018101665A1
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semiconductor
magnetization
coating film
ferromagnetic
manufacturing
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PCT/KR2017/013201
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French (fr)
Korean (ko)
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김학수
백승배
이수완
김태호
김대현
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선문대학교 산학협력단
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/01—Manufacture or treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method of manufacturing a semiconductor coating film using magnetization that can improve the semiconductor performance by increasing the electron mobility of the semiconductor and lowering the bandgap energy compared to before the magnetization by using a process of magnetizing the semiconductor containing the ferromagnetic material.
  • Solar cells have been continuously developed through research and development. Recently, various solar cells such as organic solar cells, compound solar cells, thin film solar cells, silicon solar cells, and dye solar cells have been developed. Silicon solar cells now make up the majority of the solar energy to electrical energy. However, electrical energy using silicon solar cells has a problem in that the cost of generating power is higher than that of other power sources such as hydro, nuclear, and thermal power. Therefore, in order to solve the price problem of existing silicon solar cells, interest in thin film solar cells has recently increased rapidly, and research on thin film solar cells with price competitiveness as future solar cell technology has been concentrated. Among them, dye-sensitized solar cells have become more interesting because they can use cheap organic dyes and nanotechnology to achieve higher energy efficiency than other types of thin-film solar cells.
  • the advantages of dye-sensitized solar cells are as follows: First, the production cost is low due to the use of TiO 2 and dyes (expected unit price up to 1/5 of silicon solar cells) and the manufacturing process is simple. You can expect. Second, carbon dioxide emissions are reduced by using non-toxic materials. Third, the light transmittance and various colors as well as light and flexible, it is possible to apply external building solar power generation system, such as SEV (Sunrise Energy Ventures), BIPV (Building Integrated Photovoltaic) System. Fourth, it can be used even in low light or cloudy days, allowing for indoor power generation and excellent performance in the north. The efficiency decreases with the change of the incident angle, and the efficiency increases with increasing temperature.
  • SEV Small Energy Ventures
  • BIPV Building Integrated Photovoltaic
  • the commercial efficiency of the dye-sensitized solar cell is 4-7%, which is difficult to commercialize due to low efficiency compared to the commercial efficiency of about 14-17% of the silicon solar cell, and there was a problem of insufficient stability.
  • An object of the present invention is to provide a method for producing a material for improving the semiconductor performance of a semiconductor mixture containing a ferromagnetic material, and another object is to provide a solar cell such as a dye-sensitized solar cell using an improved performance semiconductor mixture It is to provide a method for manufacturing an electrophoretic material for solar cells for improving the performance of the electron transfer material of the cell.
  • a semiconductor composition comprising a semiconductor, mixing a ferromagnetic material in the semiconductor composition to form a semiconductor-ferromagnetic composite, a semiconductor-ferromagnetic coating film on a substrate using the semiconductor-ferromagnetic composite It is achieved by a method of manufacturing a semiconductor coating film using an improved magnetization electron mobility including the step of forming, magnetizing the semiconductor-ferromagnetic coating layer.
  • the semiconductor may be a photocatalyst material.
  • Between the magnetizing the coating layer and the step of forming the coating film may not include the step of forming or bonding another material layer on the coating film.
  • the photocatalyst material may be at least one selected from TiO 2 , ZnO, CdS, ZrO 2 , V 2 O 3 , WO 3 , and perovskite, or two or more composites.
  • the ferromagnetic material may be at least one selected from among compounds containing Fe 3 O 4 , Mn, Co, and Si, or two or more complexes.
  • the shape of the semiconductor-ferromagnetic composite may be at least one selected from a paste, a mixed solution, a slurry, a sol, and a gel.
  • the magnetization may include applying a magnetic force of 0.5 Tesla (T) or more.
  • the magnetization may be performed using a vibration sample magnetometer (VSM).
  • VSM vibration sample magnetometer
  • the electron mobility is achieved by an electrode layer including a coating film prepared by a semiconductor coating film manufacturing method using the improved magnetization.
  • the electron mobility is achieved by a dye-sensitized solar cell comprising a coating film prepared by a semiconductor coating film manufacturing method using the improved magnetization.
  • the present invention relates to a method for manufacturing a semiconductor coating film using magnetization, and the prepared coating film has a lower bandgap energy than the coating film not subjected to the magnetization step, thereby improving semiconductor performance and photocatalytic performance, and when manufacturing a solar cell electrode using the same.
  • the improvement of the power generation efficiency of a solar cell can be expected.
  • 1 is a graph of the amount of current before and after magnetization according to an embodiment of the present invention.
  • 3 is a bandgap energy graph after magnetization according to an embodiment of the present invention.
  • Figure 4 is a photograph showing a dye-sensitized solar cell electrode according to an embodiment of the present invention.
  • the semiconductor in the semiconductor composition including the semiconductor means a general semiconductor material, but more preferably, a semiconductor material that can be utilized for dye-sensitized solar cell electrodes. It may also be a semiconductor material exhibiting photocatalytic properties. Representatively, there is TiO 2 , TiO 2 is well known for photocatalytic properties, but is also widely used in electrode materials of dye-sensitized solar cells, and is well known photocatalytic semiconductor material for semiconductor performance. In addition, it can be utilized as a material by the manufacturing method of this invention also for the use of various photocatalysts, a semiconductor, etc.
  • the photocatalytic material may be TiO 2 , or at least one selected from ZnO, CdS, ZrO 2 , V 2 O 3 , WO 3 , and perovskite, or two or more composites.
  • the ferromagnetic material in the step of making a semiconductor-ferromagnetic composite by mixing the ferromagnetic material with the semiconductor composition is not particularly limited as long as it is a general ferromagnetic material, but is preferably a material that forms a solid solution or is doped with the semiconductor material.
  • the experiment was conducted using Fe 3 O 4 , but is not particularly limited, and materials such as Fe 2 O 3 , Ni, and Fe are expected to show similar results.
  • the shape of the semiconductor-ferromagnetic composite is not particularly limited as long as it is a shape for making a coating film in a later step.
  • a paste phase mixed with an electrode material is preferable, and a slurry, a brush, a gel, and the like are also possible. Depending on the quality of the mixture, the mixed solution form may be good.
  • forms such as sol and gel are preferable and may be included in a composition such as paint.
  • the magnetization step which is the most important step in the present invention, is largely different from that of the conventional techniques that do not describe a special treatment even after forming the ferromagnetic mixture, and magnetization after device formation in a semiconductor using a magnetization material such as in MRAM. It's also different from going through the steps.
  • the magnetization step in the present invention is characterized in that it does not include the step of forming or bonding another material layer on the coating film between the magnetizing the coating layer and the step of forming the coating film. That is, after the coating layer is formed, it is performed before binding to the other layer or covering the coating layer with another material.
  • the magnetization in the magnetization step is preferably to apply a magnetic force of 0.5 Tesla (T) or more. If the magnetization is smaller than 0.5 Tesla, the electron mobility of the semiconductor including the ferromagnetic material is improved, and the difference before and after the magnetization step is not large. In this experiment, magnetization was carried out by increasing the magnetic force up to the 2 Tesla range, and the stronger the magnetic force, the higher the electron mobility. Therefore, the experiments of the present invention confirmed an increase in electron mobility in the range of 0.5 Tesla to 2 Tesla, and through this, the bandgap energy was lowered, thereby improving semiconductor performance. As long as the device or other device is not overwhelming, electron mobility is expected to be improved even in the higher Tesla range.
  • T 0.5 Tesla
  • VSM vibration sample magnetometer
  • This is generally used as a device for measuring the magnetic force of the sample, but the magnetic force is applied to the sample for the measurement of the magnetic force, in the present invention is used as a device for applying a magnetic force to the coating film by changing the use of the conventional vibration sample magnetometer It was.
  • any device that can apply magnetic force to a sample in a similar principle to a vibrating sample magnetometer is not particularly limited.
  • the electrode layer for the solar cell was formed using the coating film prepared by the semiconductor coating film manufacturing method using the magnetization, by manufacturing a dye-sensitized solar cell using the electrode layer formed as described above by measuring the electrical conversion efficiency of the solar cell It was confirmed that the electrical change efficiency is improved compared to the dye-sensitized solar cell.
  • TiO 2 paste for electrodes To produce a TiO 2 paste for electrodes according to the general method for producing TiO 2 paste. Mixture of 5 ⁇ 30 wt% Fe 3 O 4 to TiO 2 paste to prepare the Fe 3 O 4 / TiO 2 paste. To prepare the FTO Glass to coat the paste, the paste is coated on the prepared FTO Glass. The coated paste is calcined for 1 hour in a calciner at 450 ° C., followed by further natural drying after calcination to form one electrode. 0.03 g of N719dye is mixed with 100 ml of ethanol for 24 hours to prepare a dye solution. The formed one electrode and the dye solution are placed in the same container and adsorbed for 24 hours while blocking light.
  • One electrode adsorbed is magnetized to 1.5T (Tesla) using VSM equipment.
  • the counter electrode to be combined with the magnetized one electrode is prepared by coating Pt paste and calcining at 450 ° C. for 1 hour to dry naturally.
  • the magnetized one electrode and the counter electrode were bonded at 100 ° C. for 5 minutes. After the injection of electrolyte to finish the dye-sensitized solar cell manufacturing.
  • FIG. 1 is a graph showing the results of measuring the amount of current using a TiO 2 coating film impregnated with 10 wt% Fe 3 O 4 before and after magnetization. Before the magnetization, the current was about 1.3 mA, but after the magnetization, the current was about 2.7 to 3.0 mA, indicating that the current amount was improved.
  • FIG. 2 and 3 are graphs showing the change in the bandgap energy before and after magnetization, respectively, FIG. 2 is a graph measuring the bandgap energy of the coating film using only TiO 2 photocatalyst, and FIG. 3 is 10 wt% of Fe 3 O 4. Is a graph measuring bandgap energy after magnetization of the impregnated TiO 2 coating layer.
  • the semiconductor manufactured by the electrode manufacturing method through magnetization was reduced in bandgap energy, and thus, the result of measuring the photoelectric conversion efficiency of the solar cell was improved.

Abstract

The present invention relates to a method for manufacturing a semiconductor coating film by using magnetization, the method being capable of improving performance, over that of pre-magnetization, of a semiconductor by enhancing electron mobility of the semiconductor and lowering band gap energy, by using a process for magnetizing the semiconductor containing a ferromagnetic material. The present invention relates to the method for manufacturing the semiconductor coating film by using the magnetization, the manufactured coating film has lower band gap energy than a coating film, which do not pass through a magnetization step, such that semiconductor performance and photocatalytic performance are improved, and the improvement of power generation efficiency of a solar cell can be expected when an electrode for solar cell is manufactured by using the same method.

Description

자화를 이용한 반도체 코팅막 제조방법Method of manufacturing semiconductor coating film using magnetization
본 발명은 강자성체가 포함된 반도체를 자화시키는 공정을 이용하여 자화 전에 비하여 반도체의 전자 이동도를 높여주고 밴드갭 에너지를 낮추어 주어 반도체 성능을 향상시킬 수 있는 자화를 이용한 반도체 코팅막 제조방법에 관한 것이다.The present invention relates to a method of manufacturing a semiconductor coating film using magnetization that can improve the semiconductor performance by increasing the electron mobility of the semiconductor and lowering the bandgap energy compared to before the magnetization by using a process of magnetizing the semiconductor containing the ferromagnetic material.
최근 석유에너지의 사용으로 인한 지구의 온난화, 기상이변, 그리고 일본 후쿠시마 원자력 발전소에서 발생된 사고를 통해 나타난 원자력 에너지처럼 환경적 재앙을 일으키지 않는 새로운 에너지에 대하여 전 세계적으로 주목을 하고 있으며 또한 이에 대해 활발한 연구가 진행되고 있다. 특히 청정에너지 중 태양의 빛 에너지를 이용하는 태양광 발전은 연료가 필요 없어 환경적 공해를 발생시키지 않고 또한 소음을 발생시키지 않으며 작동이 간편하고 무인화가 용이하며 에너지 생산에 따른 부산물이 나오지 않는 장점을 가지고 있어서 청정에너지 중 가장 주목받는 에너지라고 할 수 있다. The world is paying attention to new energy that does not cause environmental disasters such as global warming due to the use of petroleum energy, extreme weather, and nuclear energy caused by an accident at Fukushima nuclear power plant in Japan. Is going on. In particular, photovoltaic power generation using solar light energy among clean energy does not need fuel and thus does not generate environmental pollution, generates no noise, is simple to operate, easy to unmanned, and does not produce by-products due to energy production. In this regard, it can be said to be the most noticeable energy among clean energy.
태양전지는 연구개발을 통해 지속적으로 발전하였고 최근에는 유기물 태양전지, 화합물 태양전지, 박막형 태양전지, 실리콘 태양전지, 염료형 태양전지 등 다양한 태양전지가 개발되었다. 태양에너지를 전기에너지로 변환하는 것으로 실리콘 태양전지가 현재 대부분을 차지한다. 그러나 실리콘 태양전지를 활용한 전기에너지는 수력, 원자력, 화력 등 다른 발전에너지원에 비해 발전 단가가 높다는 문제점이 있다. 따라서 기존 실리콘 태양전지의 가격 문제점을 해결하고자 최근 들어 박막 태양전지에 대한 관심이 급증하고 있으며 미래의 태양전지 기술로 가격 경쟁력이 있는 박막 태양전지 연구가 집중되고 있다. 이 중 특히 염료 감응 태양전지는 값싼 유기 염료와 나노 기술을 이용하여 저렴하면서도 다른 종류의 박막 태양전지들보다 고도의 에너지 효율을 낼 수 있기 때문에 좀 더 관심을 갖게 되었다. Solar cells have been continuously developed through research and development. Recently, various solar cells such as organic solar cells, compound solar cells, thin film solar cells, silicon solar cells, and dye solar cells have been developed. Silicon solar cells now make up the majority of the solar energy to electrical energy. However, electrical energy using silicon solar cells has a problem in that the cost of generating power is higher than that of other power sources such as hydro, nuclear, and thermal power. Therefore, in order to solve the price problem of existing silicon solar cells, interest in thin film solar cells has recently increased rapidly, and research on thin film solar cells with price competitiveness as future solar cell technology has been concentrated. Among them, dye-sensitized solar cells have become more interesting because they can use cheap organic dyes and nanotechnology to achieve higher energy efficiency than other types of thin-film solar cells.
염료감응 태양전지의 장점으로는 첫째, TiO2와 염료의 사용으로 제작비용이 저렴(실리콘 태양전지 대비 예상단가 최대 1/5)하고 제조공정이 간편하여 차세대 태양전지로 범용화가 되어 시장선점과 활성화를 기대할 수 있다. 둘째, 무독성 소재를 사용하여 이산화탄소 배출이 감소한다는 것이다. 셋째, 광 투과성이 높고 다양한 색상을 나타낼 뿐만 아니라 가볍고 유연성이 있어 SEV(Sunrise Energy Ventures), BIPV(Building Integrated Photovoltaic) System 등과 같은 건물 외장형 태양광 발전시스템의 적용이 가능하다는 것이다. 넷째, 빛이 약하거나 흐린 날에도 사용할 수 있어 실내발전이 가능하고 북향에서도 성능이 우수하여 환경제약을 크게 받지 않는다는 것이다. 입사각 변화에 따라 효율감소가 적으며, 온도가 상승할수록 효율 또한 증가한다.The advantages of dye-sensitized solar cells are as follows: First, the production cost is low due to the use of TiO 2 and dyes (expected unit price up to 1/5 of silicon solar cells) and the manufacturing process is simple. You can expect. Second, carbon dioxide emissions are reduced by using non-toxic materials. Third, the light transmittance and various colors as well as light and flexible, it is possible to apply external building solar power generation system, such as SEV (Sunrise Energy Ventures), BIPV (Building Integrated Photovoltaic) System. Fourth, it can be used even in low light or cloudy days, allowing for indoor power generation and excellent performance in the north. The efficiency decreases with the change of the incident angle, and the efficiency increases with increasing temperature.
이러한 장점을 가지고 있는 반면에 염료감응 태양전지의 상업용 효율이 4~7%로 실리콘 태양전지의 상업용 효율 약 14~17%에 비해 낮은 효율로 인해 상용화가 어려우며, 안정성이 부족한 문제가 있었다. On the other hand, the commercial efficiency of the dye-sensitized solar cell is 4-7%, which is difficult to commercialize due to low efficiency compared to the commercial efficiency of about 14-17% of the silicon solar cell, and there was a problem of insufficient stability.
본 발명의 목적은, 강자성체가 포함된 반도체 혼합물의 반도체 성능을 개선하기 위한 물질 제조하기 위한 방법을 제공하기 위한 것이며, 또 다른 목적은 개선된 성능의 반도체 혼합물을 이용하여 염료감응 태양전지 등의 태양전지의 전자 이동 물질의 성능을 개선하기 위한 태양전지용 전자이동 물질을 제조하기 위한 방법을 제공하는 것이다.An object of the present invention is to provide a method for producing a material for improving the semiconductor performance of a semiconductor mixture containing a ferromagnetic material, and another object is to provide a solar cell such as a dye-sensitized solar cell using an improved performance semiconductor mixture It is to provide a method for manufacturing an electrophoretic material for solar cells for improving the performance of the electron transfer material of the cell.
상기 목적을 달성하기 위하여, 반도체를 포함하는 반도체조성물을 마련하는 단계, 상기 반도체조성물에 강자성체를 혼합하여 반도체-강자성체 복합물을 만드는 단계, 상기 반도체-강자성체 복합물을 이용하여 기재 상에 반도체-강자성체 코팅막을 형성하는 단계, 상기 반도체-강자성체 코팅층을 자화시키는 단계를 포함하는 전자이동도가 향상된 자화를 이용한 반도체 코팅막 제조방법으로 달성된다. In order to achieve the above object, to provide a semiconductor composition comprising a semiconductor, mixing a ferromagnetic material in the semiconductor composition to form a semiconductor-ferromagnetic composite, a semiconductor-ferromagnetic coating film on a substrate using the semiconductor-ferromagnetic composite It is achieved by a method of manufacturing a semiconductor coating film using an improved magnetization electron mobility including the step of forming, magnetizing the semiconductor-ferromagnetic coating layer.
상기 반도체는 광촉매 물질일 수 있다. The semiconductor may be a photocatalyst material.
상기 코팅층을 자화시키는 단계와 상기 코팅막을 형성하는 단계 사이에는 상기 코팅막 상에 다른 물질층을 형성하거나 결합하는 단계를 포함하지 않을 수 있다. Between the magnetizing the coating layer and the step of forming the coating film may not include the step of forming or bonding another material layer on the coating film.
상기 광촉매 물질은 TiO2, ZnO, CdS, ZrO2, V2O3, WO3, 및 페로브스카이트 중 선택되는 적어도 하나이거나 또는 둘 이상의 복합체일 수 있다. The photocatalyst material may be at least one selected from TiO 2 , ZnO, CdS, ZrO 2 , V 2 O 3 , WO 3 , and perovskite, or two or more composites.
상기 강자성체는 Fe3O4, Mn, Co, 및 Si의 원소가 포함된 화합물 중 선택되는 적어도 하나이거나 또는 둘 이상의 복합체일 수 있다. The ferromagnetic material may be at least one selected from among compounds containing Fe 3 O 4 , Mn, Co, and Si, or two or more complexes.
상기 반도체-강자성체 복합물의 형상은 페이스트, 혼합용액, 슬러리, 솔 및 겔 중 선택되는 적어도 하나일 수 있다. The shape of the semiconductor-ferromagnetic composite may be at least one selected from a paste, a mixed solution, a slurry, a sol, and a gel.
상기 자화는 0.5 테슬라(T) 이상의 자력을 가하는 단계를 포함할 수 있다. The magnetization may include applying a magnetic force of 0.5 Tesla (T) or more.
상기 자화는 진동 샘플 자력계(VSM)를 이용하여 수행할 수 있다. The magnetization may be performed using a vibration sample magnetometer (VSM).
상기 목적을 달성하기 위한 또 다른 해결수단으로서, 상기의 전자이동도가 향상된 자화를 이용한 반도체 코팅막 제조방법에 의해 제조된 코팅막을 포함하는 전극층에 의해 달성된다. As another solution for achieving the above object, the electron mobility is achieved by an electrode layer including a coating film prepared by a semiconductor coating film manufacturing method using the improved magnetization.
상기 목적을 달성하기 위한 또 다른 해결수단으로서, 상기의 전자이동도가 향상된 자화를 이용한 반도체 코팅막 제조방법에 의해 제조된 코팅막을 포함하는 염료감응 태양전지에 의해 달성된다. As another solution for achieving the above object, the electron mobility is achieved by a dye-sensitized solar cell comprising a coating film prepared by a semiconductor coating film manufacturing method using the improved magnetization.
본 발명은 자화를 이용한 반도체 코팅막 제조방법에 관한 것으로서, 제조된 코팅막은 자화단계를 거치지 않은 코팅막에 비해 밴드갭 에너지가 낮아져 반도체 성능 및 광촉매 성능이 개선되며, 이를 이용하여 태양전지용 전극을 제조할 경우 태양전지의 발전 효율의 개선을 기대할 수 있다. The present invention relates to a method for manufacturing a semiconductor coating film using magnetization, and the prepared coating film has a lower bandgap energy than the coating film not subjected to the magnetization step, thereby improving semiconductor performance and photocatalytic performance, and when manufacturing a solar cell electrode using the same. The improvement of the power generation efficiency of a solar cell can be expected.
도 1은 본 발명의 일실시예에 따른 자화 전후의 전류량 그래프이다. 1 is a graph of the amount of current before and after magnetization according to an embodiment of the present invention.
도 2는 본 발명의 일실시예에 따른 자화 전의 밴드갭 에너지 그래프이다. 2 is a bandgap energy graph before magnetization according to an embodiment of the present invention.
도 3은 본 발명의 일실시예에 따른 자화 후의 밴드갭 에너지 그래프이다. 3 is a bandgap energy graph after magnetization according to an embodiment of the present invention.
도 4는 본 발명의 일실시예에 따른 염료감응 태양전지 전극을 나타낸 사진이다. Figure 4 is a photograph showing a dye-sensitized solar cell electrode according to an embodiment of the present invention.
이하 도면을 참조하여 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
첨부된 도면은 본 발명의 기술적 사상을 더욱 구체적으로 설명하기 위하여 도시한 일 예에 불과하므로 본 발명의 사상이 첨부된 도면에 한정되는 것은 아니다.The accompanying drawings are only examples as illustrated in order to explain the technical idea of the present invention in more detail, and thus the spirit of the present invention is not limited to the accompanying drawings.
본 발명의 실시예에 따른 자화를 이용한 반도체 코팅막 제조방법은 다음과 같다:Method for producing a semiconductor coating film using magnetization according to an embodiment of the present invention is as follows:
a) 반도체를 포함하는 반도체조성물을 마련하는 단계; a) preparing a semiconductor composition comprising a semiconductor;
b) 상기 반도체조성물에 강자성체를 혼합하여 반도체-강자성체 복합물을 만드는 단계; b) mixing the ferromagnetic material with the semiconductor composition to form a semiconductor-ferromagnetic composite;
c) 상기 제2단계의 반도체-강자성체 복합물을 이용하여 기재 상에 반도체-강자성체 코팅막을 형성하는 단계; c) forming a semiconductor-ferromagnetic coating film on the substrate using the semiconductor-ferromagnetic composite of the second step;
d) 상기 반도체-강자성체 코팅층을 자화시키는 단계.d) magnetizing the semiconductor-ferromagnetic coating layer.
상기 반도체를 포함하는 반도체조성물에서의 반도체는 일반적인 반도체 물질을 의미하나, 더욱 바람직하게는 염료감응 태양전지 전극에 활용될 수 있는 반도체 물질이면 더욱 좋다. 또한, 광촉매 특성을 나타내는 반도체 물질일 수도 있다. 대표적으로는 TiO2가 있으며, TiO2는 광촉매 특성으로 잘 알려져 있으나, 염료감응 태양전지의 전극재료에서도 많이 활용되며, 반도체 성능에 대해서도 잘 알려진 광촉매 특성 반도체 물질이다. 이외에도 각종 광촉매나 반도체 등의 용도로도 본 발명의 제조방법에 의한 재료로 활용 가능하다. 상기 광촉매 물질은 TiO2를 비롯하여 ZnO, CdS, ZrO2, V2O3, WO3, 및 페로브스카이트 중 선택되는 적어도 하나이거나 또는 둘 이상의 복합체도 가능하다. The semiconductor in the semiconductor composition including the semiconductor means a general semiconductor material, but more preferably, a semiconductor material that can be utilized for dye-sensitized solar cell electrodes. It may also be a semiconductor material exhibiting photocatalytic properties. Representatively, there is TiO 2 , TiO 2 is well known for photocatalytic properties, but is also widely used in electrode materials of dye-sensitized solar cells, and is well known photocatalytic semiconductor material for semiconductor performance. In addition, it can be utilized as a material by the manufacturing method of this invention also for the use of various photocatalysts, a semiconductor, etc. The photocatalytic material may be TiO 2 , or at least one selected from ZnO, CdS, ZrO 2 , V 2 O 3 , WO 3 , and perovskite, or two or more composites.
상기 반도체조성물에 강자성체를 혼합하여 반도체-강자성체 복합물을 만드는 단계에서의 강자성체는 일반적인 강자성체 물질이면 특별히 제한되지는 않으나, 반도체 물질에 고용체를 형성하거나 도핑되는 물질이 바람직하다. 본 발명에서는 Fe3O4를 이용하여 실험을 진행하였으나 특별히 한정되지는 않으며, Fe2O3, Ni, 및 Fe 등의 물질도 유사한 결과를 나타낼 것으로 기대된다. The ferromagnetic material in the step of making a semiconductor-ferromagnetic composite by mixing the ferromagnetic material with the semiconductor composition is not particularly limited as long as it is a general ferromagnetic material, but is preferably a material that forms a solid solution or is doped with the semiconductor material. In the present invention, the experiment was conducted using Fe 3 O 4 , but is not particularly limited, and materials such as Fe 2 O 3 , Ni, and Fe are expected to show similar results.
상기 반도체-강자성체 복합물의 형상은 이후 단계에서 코팅막을 만들기 위한 형상이면 특별히 제한되지는 않는다. 전극 제조 등을 위해서는 전극물질과 혼합한 페이스트 상이 바람직하며, 슬러리나 솔, 젤 등도 가능하다. 혼합물질에 따라서 혼합용액 형태가 좋을 수도 있다. 오염물 분해, 수소 제조 등의 광촉매 특성을 이용하기 위한 용도의 코팅막을 제조하기 위해서는 솔 및 젤 등의 형태가 바람직하며 도료 등의 조성물에 포함될 수도 있다. The shape of the semiconductor-ferromagnetic composite is not particularly limited as long as it is a shape for making a coating film in a later step. For electrode production or the like, a paste phase mixed with an electrode material is preferable, and a slurry, a brush, a gel, and the like are also possible. Depending on the quality of the mixture, the mixed solution form may be good. In order to manufacture a coating film for utilizing photocatalytic properties such as decomposition of contaminants and hydrogen production, forms such as sol and gel are preferable and may be included in a composition such as paint.
본 발명에서의 가장 중요한 단계인 자화 단계는, 종래의 기술들이 강자성체 혼합물을 형성한 후에도 별다른 처리에 대해 기술하지 않는 것과 크게 차별화되며, MRAM 등의 기술 등에서 자화물질을 이용한 반도체에서 디바이스 형성 이후에 자화 단계를 거치는 것과도 차별화된다. 본 발명에서의 자화단계는 상기 코팅층을 자화시키는 단계와 상기 코팅막을 형성하는 단계 사이에 상기 코팅막 상에 다른 물질층을 형성하거나 결합하는 단계를 포함하지 않는 것을 특징으로 한다. 즉 코팅층 형성 후 다른 층과의 결합 또는 다른 물질로 코팅층을 커버하기 전에 수행하는 것을 특징으로 한다. The magnetization step, which is the most important step in the present invention, is largely different from that of the conventional techniques that do not describe a special treatment even after forming the ferromagnetic mixture, and magnetization after device formation in a semiconductor using a magnetization material such as in MRAM. It's also different from going through the steps. The magnetization step in the present invention is characterized in that it does not include the step of forming or bonding another material layer on the coating film between the magnetizing the coating layer and the step of forming the coating film. That is, after the coating layer is formed, it is performed before binding to the other layer or covering the coating layer with another material.
상기 자화 단계에서 자화는 0.5 테슬라(T) 이상의 자력을 가하는 것이 바람직하다. 0.5 테슬라보다 작게 자화시키게 되면, 강자성체를 포함한 반도체의 전자 이동도 향상이 약하게 이루어져 자화 단계 전후의 차이가 크지 않게 된다. 본 실험에서는 2 테슬라 범위까지 자력을 증가시키며 자화를 하였으며, 자력이 강할수록 전자이동도가 증가함을 확인하였다. 따라서 본 발명의 실험을 통해서 0.5 테슬라 내지 2 테슬라 범위에서의 전자이동도 증가를 확인하였고, 이를 통해 밴드갭 에너지가 낮아져 반도체 성능의 개선을 기대할 수 있었다. 디바이스나 다른 장치에 무리가 가지 않는 한은 더 높은 테슬라 범위에서도 전자 이동도 개선의 효과가 있을 것으로 예상된다. The magnetization in the magnetization step is preferably to apply a magnetic force of 0.5 Tesla (T) or more. If the magnetization is smaller than 0.5 Tesla, the electron mobility of the semiconductor including the ferromagnetic material is improved, and the difference before and after the magnetization step is not large. In this experiment, magnetization was carried out by increasing the magnetic force up to the 2 Tesla range, and the stronger the magnetic force, the higher the electron mobility. Therefore, the experiments of the present invention confirmed an increase in electron mobility in the range of 0.5 Tesla to 2 Tesla, and through this, the bandgap energy was lowered, thereby improving semiconductor performance. As long as the device or other device is not overwhelming, electron mobility is expected to be improved even in the higher Tesla range.
본 발명에서 코팅막에 자화를 한 장비는 진동 샘플 자력계(VSM)였다. 이는 샘플의 자력을 측정하는 장비로 사용되는 것이 일반적이지만, 자력의 측정을 위해 샘플에 자력을 부여하게 되므로, 본 발명에서는 종래의 진동 샘플 자력계의 용도를 변화시켜 코팅막에 자력을 부여하는 장비로 활용하였다. 하지만, 진동 샘플 자력계와 유사한 원리로 샘플에 자력을 부여할 수 있는 장비라면 특별히 제한되지 않는다. Equipment to magnetize the coating film in the present invention was a vibration sample magnetometer (VSM). This is generally used as a device for measuring the magnetic force of the sample, but the magnetic force is applied to the sample for the measurement of the magnetic force, in the present invention is used as a device for applying a magnetic force to the coating film by changing the use of the conventional vibration sample magnetometer It was. However, any device that can apply magnetic force to a sample in a similar principle to a vibrating sample magnetometer is not particularly limited.
본 발명에서는 상기 자화를 이용한 반도체 코팅막 제조방법에 의해 제조된 코팅막을 이용하여 태양전지용 전극층을 형성하였으며, 이렇게 형성된 전극층을 이용하여 염료감응 태양전지를 제조하여 태양전지의 전기변환 효율을 측정하여 종래의 염료감응 태양전지에 비해 전기변화 효율이 개선됨을 확인하였다. In the present invention, the electrode layer for the solar cell was formed using the coating film prepared by the semiconductor coating film manufacturing method using the magnetization, by manufacturing a dye-sensitized solar cell using the electrode layer formed as described above by measuring the electrical conversion efficiency of the solar cell It was confirmed that the electrical change efficiency is improved compared to the dye-sensitized solar cell.
실험예Experimental Example
일반적인 TiO2 페이스트 제조방법에 따라 전극용 TiO2 페이스트를 제조한다. TiO2 페이스트에 5~30 wt% Fe3O4 를 혼합하여 Fe3O4/TiO2 페이스트를 제조한다. 상기 페이스트를 코팅하기 위해 FTO Glass를 준비하며, 준비된 FTO Glass 상에 상기 페이스트를 코팅한다. 코팅된 페이스트는 450℃의 소성기에서 1시간 동안 하소하며, 하소 후 자연 건조를 추가적으로 더 수행하여 일 전극을 형성한다. N719dye 0.03g을 에탄올 100ml에 24시간 혼합하여 염료용액을 준비한다. 상기 형성된 일전극과 염료용액을 같은 용기에 담고 빛을 차단한 상태에서 24시간 흡착시킨다. 흡착시킨 일 전극을 VSM 장비를 활용하여 1.5T(Tesla)로 조립 전 자화를 시킨다. 자화된 일 전극과 결합시킬 상대전극을 Pt 페이스트를 코팅한 후 450℃ 소성기에서 1시간 하소하여 자연건조 시켜 제조한다. 자화된 일 전극과 상대전극을 100℃에서 5분간 설린 접합시킨다. 이후 전해질 주입 후 설린으로 마감작업을 하여 염료감응 태양전지를 제조한다. To produce a TiO 2 paste for electrodes according to the general method for producing TiO 2 paste. Mixture of 5 ~ 30 wt% Fe 3 O 4 to TiO 2 paste to prepare the Fe 3 O 4 / TiO 2 paste. To prepare the FTO Glass to coat the paste, the paste is coated on the prepared FTO Glass. The coated paste is calcined for 1 hour in a calciner at 450 ° C., followed by further natural drying after calcination to form one electrode. 0.03 g of N719dye is mixed with 100 ml of ethanol for 24 hours to prepare a dye solution. The formed one electrode and the dye solution are placed in the same container and adsorbed for 24 hours while blocking light. One electrode adsorbed is magnetized to 1.5T (Tesla) using VSM equipment. The counter electrode to be combined with the magnetized one electrode is prepared by coating Pt paste and calcining at 450 ° C. for 1 hour to dry naturally. The magnetized one electrode and the counter electrode were bonded at 100 ° C. for 5 minutes. After the injection of electrolyte to finish the dye-sensitized solar cell manufacturing.
도 1은 자화를 수행하기 전후의 10 wt%의 Fe3O4가 함침된 TiO2 코팅막을 이용하여 전류량 측정을 한 결과를 나타낸 그래프이다. 자화를 수행하기 전 전류는 약 1.3mA를 나타냈으나, 자화를 수행한 이후에는 약 2.7에서 3.0 mA 사이의 값을 나타내어 전류량이 개선된 것을 확인하였다. 1 is a graph showing the results of measuring the amount of current using a TiO 2 coating film impregnated with 10 wt% Fe 3 O 4 before and after magnetization. Before the magnetization, the current was about 1.3 mA, but after the magnetization, the current was about 2.7 to 3.0 mA, indicating that the current amount was improved.
도 2와 도 3은 자화 전후의 밴드갭 에너지의 변화를 각각 나타낸 그래프로서, 도 2는 TiO2 광촉매 만을 이용한 코팅막의 밴드갭 에너지를 측정한 그래프이고, 도 3은 10 wt%의 Fe3O4가 함침된 TiO2 코팅막의 자화 이후 밴드갭 에너지를 측정한 그래프이다. 2 and 3 are graphs showing the change in the bandgap energy before and after magnetization, respectively, FIG. 2 is a graph measuring the bandgap energy of the coating film using only TiO 2 photocatalyst, and FIG. 3 is 10 wt% of Fe 3 O 4. Is a graph measuring bandgap energy after magnetization of the impregnated TiO 2 coating layer.
이와 같이 자화를 통한 전극제조 방법으로 제조된 반도체는 밴드갭 에너지가 감소하였고, 이를 통해 태양전지의 광전변환효율을 측정한 결과 개선되었음을 확인할 수 있었다. As described above, the semiconductor manufactured by the electrode manufacturing method through magnetization was reduced in bandgap energy, and thus, the result of measuring the photoelectric conversion efficiency of the solar cell was improved.
전술한 실시예들은 본 발명을 설명하기 위한 예시로서, 본 발명이 이에 한정되는 것은 아니다. 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 이로부터 다양하게 변형하여 본 발명을 실시하는 것이 가능할 것이므로, 본 발명의 기술적 보호범위는 첨부된 특허청구범위에 의해 정해져야 할 것이다. The above-described embodiments are examples for explaining the present invention, but the present invention is not limited thereto. Those skilled in the art to which the present invention pertains will be capable of carrying out the present invention by various modifications therefrom, and the technical protection scope of the present invention should be defined by the appended claims.

Claims (10)

  1. 반도체를 포함하는 반도체조성물을 마련하는 단계;Preparing a semiconductor composition comprising a semiconductor;
    상기 반도체조성물에 강자성체를 혼합하여 반도체-강자성체 복합물을 만드는 단계;Mixing a ferromagnetic material with the semiconductor composition to form a semiconductor-ferromagnetic composite;
    상기 반도체-강자성체 복합물을 이용하여 기재 상에 반도체-강자성체 코팅막을 형성하는 단계;Forming a semiconductor-ferromagnetic coating film on a substrate using the semiconductor-ferromagnetic composite;
    상기 반도체-강자성체 코팅층을 자화시키는 단계; 를 포함하는 전자이동도가 향상된 자화를 이용한 반도체 코팅막 제조방법.Magnetizing the semiconductor-ferromagnetic coating layer; Method of manufacturing a semiconductor coating film using magnetization improved electron mobility including a.
  2. 제1항에서, In claim 1,
    상기 반도체는 광촉매 물질인 것을 특징으로 하는 전자이동도가 향상된 자화를 이용한 반도체 전극 제조방법.The semiconductor is a semiconductor electrode manufacturing method using the magnetization improved electron mobility, characterized in that the photocatalyst material.
  3. 제1항에서, In claim 1,
    상기 코팅층을 자화시키는 단계와 상기 코팅막을 형성하는 단계 사이에는 상기 코팅막 상에 다른 물질층을 형성하거나 결합하는 단계를 포함하지 않는 것을 특징으로 하는 자화를 이용한 반도체 전극 제조방법.Method of manufacturing a semiconductor electrode using magnetization, characterized in that it does not include the step of magnetizing the coating layer and the step of forming the coating film to form or bond another layer of material on the coating film.
  4. 제2항에서, In claim 2,
    상기 광촉매 물질은 TiO2, ZnO, CdS, ZrO2, V2O3, WO3, 및 페로브스카이트 중 선택되는 적어도 하나이거나 또는 둘 이상의 복합체인 것을 특징으로 하는 전자이동도가 향상된 자화를 이용한 반도체 전극 제조방법.The photocatalytic material may be at least one selected from TiO 2 , ZnO, CdS, ZrO 2 , V 2 O 3 , WO 3 , and perovskite, or two or more composites, and the electron mobility may be improved. Semiconductor electrode manufacturing method.
  5. 제1항에서, In claim 1,
    상기 강자성체는 Fe3O4, Mn, Co, 및 Si의 원소가 포함된 화합물 중 선택되는 적어도 하나이거나 또는 둘 이상의 복합체인 것을 특징으로 하는 전자이동도가 향상된 자화를 이용한 반도체 전극 제조방법.The ferromagnetic material is a semiconductor electrode manufacturing method using an improved magnetization electron mobility, characterized in that at least one selected from the group consisting of compounds containing elements of Fe 3 O 4 , Mn, Co, and Si or two or more.
  6. 제1항에서, In claim 1,
    상기 반도체-강자성체 복합물의 형상은 페이스트, 혼합용액, 슬러리, 솔 및 겔 중 선택되는 적어도 하나인 것을 특징으로 하는 전자이동도가 향상된 자화를 이용한 반도체 전극 제조방법.The shape of the semiconductor-ferromagnetic composite is at least one selected from a paste, a mixed solution, a slurry, a sol and a gel.
  7. 제1항에서, In claim 1,
    상기 자화는 0.5 테슬라(T) 이상의 자력을 가하는 단계를 포함하는 것을 특징으로 하는 전자이동도가 향상된 자화를 이용한 반도체 전극 제조방법.The magnetization is a semiconductor electrode manufacturing method using the magnetization improved electron mobility, comprising the step of applying a magnetic force of 0.5 Tesla (T) or more.
  8. 제7항에서, In claim 7,
    상기 자화는 진동 샘플 자력계(VSM)를 이용하여 수행하는 것을 특징으로 하는 전자이동도가 향상된 자화를 이용한 반도체 전극 제조방법.The magnetization is a semiconductor electrode manufacturing method using the magnetization improved electron mobility, characterized in that performed using a vibration sample magnetometer (VSM).
  9. 제1항의 방법에 의해 제조된 코팅막을 포함하는 전극층.An electrode layer comprising a coating film prepared by the method of claim 1.
  10. 제1항의 방법에 의해 제조된 코팅막을 포함하는 염료감응 태양전지. Dye-sensitized solar cell comprising a coating film prepared by the method of claim 1.
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