WO2015016399A1 - Dye sensitized solar cell photoelectrode including ba-sn-m-o semiconductor film - Google Patents

Dye sensitized solar cell photoelectrode including ba-sn-m-o semiconductor film Download PDF

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WO2015016399A1
WO2015016399A1 PCT/KR2013/006811 KR2013006811W WO2015016399A1 WO 2015016399 A1 WO2015016399 A1 WO 2015016399A1 KR 2013006811 W KR2013006811 W KR 2013006811W WO 2015016399 A1 WO2015016399 A1 WO 2015016399A1
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basno
solar cell
dye
sensitized solar
semiconductor film
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French (fr)
Korean (ko)
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홍국선
신성식
석재호
김동회
김주성
박익재
이찬우
성원모
조인선
김동욱
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서울대학교산학협력단
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    • 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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion 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
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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

Definitions

  • the present invention relates to a photoelectrode for a dye-sensitized solar cell, and more particularly to a photoelectrode of a dye-sensitized solar cell including a Ba—Sn—M—O-based oxide semiconductor film.
  • the dye-sensitized solar cell when the sunlight is absorbed by the semiconductor oxide electrode where the dye molecules are chemically adsorbed on the surface, the dye molecules emit electrons. The electrons are transferred to the transparent conductive substrate through various paths to finally generate current.
  • the manufacturing process is simpler than the conventional silicon solar cell, the stability is very high, and compared with the silicon-based solar cell has the advantage of being less affected by the amount of sunlight.
  • the cathode of the dye-sensitized solar cell is composed of an oxide semiconductor film composed of a transparent conductive film formed on a glass substrate and oxide semiconductor nanoparticles such as TiO 2 .
  • a dye polymer is provided by a method such as adsorption.
  • a positive electrode (counter electrode or counter electrode) of the dye-sensitized solar cell a material such as platinum is generally used and provided on a glass substrate. An electrolyte is provided between the negative electrode and the counter electrode.
  • the general principle of dye-sensitized solar cell is as follows. Sunlight enters the cell to excite the dye polymer to form an electron-hole pair, and the generated electrons are injected into the conduction band of the semiconductor oxide. The injected electrons are transferred to the outside through the semiconductor oxide. The electrons that transfer electric energy to the outside are combined with the holes of the dye polymer by the oxidation / reduction reaction of the electrolyte at the counter electrode.
  • an object of the present invention is to provide a novel multi-component oxide semiconductor film based on Ba—Sn—O that can replace the conventional TiO 2 film.
  • an object of the present invention is to provide a novel Ba-Sn-O-based multi-component oxide semiconductor film with improved photoelectric energy conversion efficiency of the dye-sensitized solar cell compared to the prior art.
  • the present invention to achieve the above technical problem is a conductive transparent substrate; And it provides a dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
  • BaSnO 3 M where M is doped with BaSnO 3 , Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La And at least one metal of the metal element consisting of Rh)
  • M may be Sr, Ca, and Mg, and may substitute at least a part of Ba sites in the crystal structure of BaSnO 3 .
  • M is Sb, and may replace at least a part of the Sn site in the crystal structure of BaSnO 3 .
  • M may be a metal that raises the conduction band in the band structure of BaSnO 3 .
  • M may be a metal that increases the electron concentration or hole concentration of BaSnO 3 .
  • M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content of the BaSnO 3 It may be included in 0.01 to 5 at% compared to Ba or Sn.
  • the M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content is BaSnO 3 It may be included in 0.01 to 1 at% of Ba or Sn.
  • the present invention provides a dye-sensitized solar cell electrode characterized in that the dye is adsorbed on the multi-component oxide semiconductor film.
  • the present invention to achieve the above technical problem is a conductive transparent substrate; And it provides a dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
  • the present invention to achieve the above technical problem, a conductive transparent substrate; And it provides a dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
  • M is Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh At least one metal selected from the group consisting of 0.05 ⁇ x ⁇ 0.5)
  • M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc, and Rh, the content of which is BaSnO 3 It may be included in 0.01 to 5 at% of Ba or Sn.
  • the M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content is BaSnO 3 It may be included in 0.01 to 1 at% of Ba or Sn.
  • the present invention provides a dye-sensitized solar cell electrode characterized in that the dye is adsorbed on the multi-component oxide semiconductor film.
  • the photoelectric energy conversion efficiency of the BaSnO 3 semiconductor oxide film can be improved to provide a photoelectrode capable of manufacturing a high efficiency solar cell.
  • FIG. 1 is a graph illustrating an X-ray diffraction pattern of Sr-doped BaSnO 3 powder according to a preferred embodiment of the present invention.
  • FIG. 2 is an enlarged graph of the diffraction pattern of FIG. 1.
  • FIG. 6 is a graph showing the results of measuring the characteristics of the solar cell according to a preferred embodiment of the present invention.
  • FIG. 7 is a graph showing the characteristics of the solar cell synthesized according to another embodiment of the present invention.
  • FIG. 8 is a graph illustrating a result of measuring characteristics of a solar cell according to another embodiment.
  • FIG. 9 is a graph showing the results of measuring the characteristics of the solar cell according to another embodiment.
  • the present invention provides a photoelectrode comprising a multi-component oxide semiconductor represented by the following formula (1).
  • BaSnO 3 M where M is doped with BaSnO 3 , Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La And at least one metal of the metal element consisting of Rh)
  • the metal element M of Chemical Formula 1 may substitute for Ba or Sn.
  • the doped metal elements change the band structure while maintaining the crystal structure of BaSnO 3 . More specifically, the doped metal elements raise the conduction band in the band structure of BaSnO 3, thereby improving cell characteristics of the solar cell.
  • Sr, Ca, and Mg may improve the conduction band by substituting Ba sites
  • Sb may improve the conduction band by substituting Sn sites.
  • the doped metal elements may improve cell characteristics of the solar cell by other mechanisms. That is, the doped metal element increases the electron concentration and hole concentration in the film, thereby improving the cell characteristics of the solar cell.
  • doped Zn, Pb, Ti, Mn, Sb, In, Zr, Te, Fe, Y, Sm, Sc, La, and Rh can improve solar cell characteristics as the main mechanism for increasing electron concentration.
  • doped Co and K may improve solar cell characteristics as the main mechanism for increasing hole concentration.
  • the cell characteristic enhancement mechanism by the doping elements may work at the same time.
  • the resulting composition of the semiconductor oxide film of the photoelectrode may be represented by the following Chemical Formula 2.
  • Chemical Formula 2 may be generally represented by the following Chemical Formula 3.
  • M1 is at least one element selected from the group consisting of Sr, Ca, and Mg
  • another metal element can replace the Sn site in the BaSnO3 crystal structure, and at this time, the band structure change as described above occurs.
  • Sb may be selected as a doping element to function as M2.
  • the metal element doped in the present invention may not be substituted for Ba or Sn sites, but may invade into the crystal structure.
  • the above-described dopable metal elements may be doped at least one kind.
  • SnCl 4 -5H 2 O, BaCl 2 -2H 2 O, and Sr (NO 3 ) 2 were used as raw material powders.
  • Each raw material powder was weighed and mixed so that the molar ratio of Sr: (Ba + Sr) changed in the range of 0 to 0.5, while maintaining the molar ratio of (Ba + Sr): Sn in a composition of 1: 1.
  • the mixed powder was dissolved in 30% hydrogen peroxide water (70:30 volume ratio of water and hydrogen peroxide), ammonia water was added to the mixed solution so that the pH was 9-11, and precipitated and aged for 12 hours. Subsequently, the precipitate obtained was washed and then lyophilized, and the dried powder was annealed at a temperature of 900 ° C. for about 2 hours to synthesize BaSnO 3 : Sr powder.
  • FIG. 1 is a graph illustrating an X-ray diffraction pattern of Sr-doped BaSnO 3 powder according to a preferred embodiment of the present invention.
  • FIG. 2 is an enlarged graph of the diffraction pattern of FIG. 1. Referring to the figure, it can be seen that the shift to the right side of the diffraction peak group near 30.5 degrees according to the amount of Ba added. It can be seen that the added Sr solidifies in the BaSnO 3 lattice structure without forming a secondary phase, thereby forming (Ba, Sr) SnO 3 .
  • FIG. 3 is a result of measuring UV absorption of the synthesized powder
  • FIG. 4 is a graph showing a Mott Schottky Analysis result.
  • UV absorption was measured by scanning in the 250-600 nm region with LAMBDA650 (Perkinelmer), and Mort Schottky measured 3 of the working electrode, counter electrode and reference electrode in 1M KCl electrolyte (pH 7) with Potentiostat (CHI 608C, CH Instrument). Measurement was made using an electrode system.
  • the band gap increases with the doping of Sr.
  • the conduction band rises according to the doping of Sr from FIG. 4, that is, the increase of the band gap is due to the rise of the conduction band.
  • Sr doping may change the band structure of BaSnO 3 to increase the characteristics of the solar cell, such as Voc and FF.
  • FIG. 5 is an electron micrograph of a Sr-doped BaSnO 3 powder. It can be seen from FIG. 3 that there is little change in shape or size of the powder particles with the addition of Sr. Therefore, it can be seen that the effect of the shape and size of the powder on the characteristics such as cell efficiency due to doping can be ignored.
  • BaSnO 3 Ca powder was synthesized under the same conditions as Preparation Example 1 except that the Sr source of Preparation Example 1 was replaced with Ca (NO 3 ) 2 -4H 2 O.
  • BaCO 3 , SnO 2 and MgCO 3 were used as raw powders.
  • the composition powders were weighed and mixed so that the molar ratio of Mg: (Ba + Mg) varied from 0 to 0.05 while the molar ratio of (Ba + Mg): Sn was maintained at 1: 1. .
  • the mixed powder and dispersant (polycarboxylic acid, MALIALIM AFB-1521) were mixed by ball milling in an ethanol solvent for 12 hours. The mixed slurry was dried and heat-treated for 2 hours in an air atmosphere of 1100 degrees to synthesize BaSnO 3 : Mg powder.
  • the synthesized BaSnO 3 : Mg powder showed the cubic form of the primary particles at low doping concentration (molar ratio of Mg to Ba + Mg), but the shape of the primary particles was increased as the doping concentration was increased. As it disappeared, the formation of coarse particles due to aggregation became prominent.
  • BaSnO 3 Ca powder was synthesized under the same conditions as in Preparation Example 4, except that MgCO 3 was replaced with CaCO 3 as a raw material powder.
  • BaSnO 3 Sr powder was synthesized under the same conditions as in Preparation Example 4, except that MgCO 3 was replaced with SrCO 3 as a raw material powder.
  • BaSnO 3 Zn powder was synthesized under the same conditions as in Preparation Example 4, except that MgCO 3 was replaced with ZnO as the starting powder.
  • the synthesized BaSnO 3 : Zn powder was confirmed that the shape of the primary particles changes as the doping concentration of Zn (molar ratio of Zn to Ba + Zn) increases.
  • BaCO 3 , SnO 2 and Sb 2 O 3 were used as raw material powders. At this time, the composition of the mixed powder was weighed and mixed so that the molar ratio of Sb: (Sn + Sb) varied from 0 to 0.05 while the molar ratio of Ba: (Sn + Sb) was 1: 1. . Milling, drying and heat treatment conditions were carried out under the same conditions as in Preparation Example 4 to synthesize BaSnO 3: Sb powder.
  • BaSnO 3 Sr powder prepared by Preparation Example 1 was mixed with a solution of organic terpineol and ethyl cellulose to form a paste, and the formed paste was applied onto the FTO substrate by screen printing. It was.
  • the BaSnO 3 Sr film is formed by heat treatment at 500 ° C. for 1 hour to remove the organic material of the film thus formed. The thickness of the formed film was about 10-15 micrometers.
  • the prepared film was subjected to dye (ruthenium-based N719 dye (cis-diisothiocyanato-bis (2,2-bipyridyl-4,4-dicarboxylato) ruthenium (II) bis ( The dye was adsorbed by dipping for a predetermined time in tetrabutylammonium) solution dissolved in ethanol at a concentration of 0.05 nM.
  • dye ruthenium-based N719 dye (cis-diisothiocyanato-bis (2,2-bipyridyl-4,4-dicarboxylato)
  • the dye was adsorbed by dipping for a predetermined time in tetrabutylammonium) solution dissolved in ethanol at a concentration of 0.05 nM.
  • a BaSnO 3 : Ca film was formed in the same manner as in Example 1 except that BaSnO 3 : Ca powder prepared in Preparation Example 2 was used, and the dye was adsorbed.
  • a BaSnO 3 : Mg film was formed in the same manner as in Example 1 except that BaSnO 3 : Mg powder prepared in Preparation Example 3 was used, and the dye was adsorbed.
  • a BaSnO 3 : Ca film was formed in the same manner as in Example 1 except that BaSnO 3 : Ca powder prepared in Preparation Example 4 was used, and the dye was adsorbed.
  • a BaSnO 3 : Sr film was formed in the same manner as in Example 1 except that BaSnO 3 : Sr powder prepared in Preparation Example 5 was used, and the dye was adsorbed.
  • a BaSnO 3 : Zn film was formed in the same manner as in Example 1 except that BaSnO 3 : Zn powder prepared in Preparation Example 6 was used, and the dye was adsorbed.
  • a BaSnO 3 : Sb film was formed in the same manner as in Example 1 except that BaSnO 3 : Sb powder prepared in Preparation Example 7 was used, and the dye was adsorbed.
  • the dye-sensitized solar cell was produced using the FTO board
  • the anode (relative electrode or counter electrode) of the dye-sensitized solar cell was formed by using Pt formed on the glass substrate by sputtering method, and the counter electrode and the working electrode on which the BaSnO 3 film was formed were sandwiched. After the cell was prepared by packing, it was injected into the packed cell using an iodine-based electrolyte.
  • I-V characteristics of the fabricated dye-sensitized solar cell were measured to determine current density (Jsc), Voc, fill factor (FF), and battery efficiency.
  • FIG. 6 is a graph showing the results of measuring the characteristics of the solar cell measured by using the Sr-doped photoelectrode of Example 1 as the working electrode.
  • Table 1 is a table comparing the characteristics of the solar cell (Sr20) consisting of a photoelectrode doped with 20% Sr and the solar cells (Bare1, Bare2) consisting of an undoped photoelectrode.
  • the efficiency of the cell doped with 20% Sr is about 26% increase compared to the undoped cell.
  • the efficiency of the solar cell is influenced by other factors such as the manufacturing method of the powder, the configuration of the cell, etc.
  • the present embodiment shows a case of synthesis by the solid-phase synthesis method, the absolute value of the efficiency is low.
  • the photoelectrode fabricated according to the present invention exhibits very high efficiency as compared to the undoped BaSnO 3 photoelectrode cell prepared under the same conditions.
  • FIG. 7 is a graph showing the characteristics of the solar cell measured by increasing the film thickness to 35 ⁇ 40 micrometers compared to Example 1. As can be seen in Figure 7, it can be seen that the efficiency increased with the increase of the film thickness.
  • Example 8 is a graph showing the results of measuring the characteristics of the solar cell measured by using the Ca-doped photoelectrode of Example 2 as the working electrode.
  • Jsc increases up to a small amount of Ca, such as Ca, from 2 to 3%.
  • Table 2 is a table showing the results of measuring the characteristics of the solar cell measured by using the photoelectrode prepared in Examples 3 to 6 as the working electrode. For comparison, the results of the measurement of the characteristics of a cell (bar) of an undoped photoelectrode are shown.
  • Examples 3 to 6 are used by the powder produced by the solid-phase method, showing a relatively low efficiency compared to the powder produced by the liquid phase method.
  • the phenomenon of an increase in current density also occurs by addition of Sb.
  • the doped Sb may be understood to improve cell characteristics by a mechanism of replacing a portion of Sn sites in BaSnO3 and changing band characteristics. have.
  • the improvement of cell characteristics due to the addition of Sb may be due to other mechanisms, namely, an increase in electron concentration or hole concentration.

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Abstract

A photoelectrode including a novel Ba-Sn-O-based multi-component oxide semiconductor film is disclosed. The present invention provides a dye sensitized solar cell photoelectrode comprising: a conductive transparent substrate; and a multi-component oxide semiconductor film formed on the substrate. A composition of the semiconductor film can be represented by BaSnO3 : M (here, M is a metal doped in BaSnO3 and comprising at least one metal element selected among Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La and Rh). According to the present invention, it is possible to provide a photoelectrode with which a high-efficient solar cell can be manufactured by improving a photoelectric energy conversion efficiency of a BaSnO3 semiconductor oxide film.

Description

Ｂａ－Ｓｎ－Ｍ－Ｏ 반도체막을 포함하는 염료감응 태양전지 광전극Dye-Sensitized Solar Cell Photoelectrode Containing BA-Sn-M-O Semiconductor Film
본 발명은 염료감응 태양전지용 광전극에 관한 것으로, 보다 상세하게는 Ba-Sn-M-O계 산화물 반도체막을 포함하는 염료감응 태양전지의 광전극에 관한 것이다.The present invention relates to a photoelectrode for a dye-sensitized solar cell, and more particularly to a photoelectrode of a dye-sensitized solar cell including a Ba—Sn—M—O-based oxide semiconductor film.
염료감응 태양전지는 표면에 염료분자가 화학적으로 흡착된 반도체 산화물 전극에 태양빛이 흡수되면 염료 분자가 전자를 내놓게 되는데 이 전자가 여러 경로를 통하여 투명 전도성 기판으로 전달되어 최종적으로 전류를 생성하는 원리를 이용한 전지로서, 기존의 실리콘 태양전지에 비하여 제조공정이 단순하며 안정성이 매우 높고, 실리콘계 태양전지와 비교했을 때 일광량의 영향을 적게 받는다는 장점을 갖는다.In the dye-sensitized solar cell, when the sunlight is absorbed by the semiconductor oxide electrode where the dye molecules are chemically adsorbed on the surface, the dye molecules emit electrons. The electrons are transferred to the transparent conductive substrate through various paths to finally generate current. As a battery using, the manufacturing process is simpler than the conventional silicon solar cell, the stability is very high, and compared with the silicon-based solar cell has the advantage of being less affected by the amount of sunlight.
염료감응 태양전지의 음극은 유리기판상에 형성된 투명 도전막과 TiO2와 같은 산화물 반도체 나노 입자로 이루어진 산화물 반도체막으로 구성된다. 상기 산화물 반도체막 상에는 염료 고분자가 흡착 등의 방법으로 제공된다. 상기 염료 감응 태양 전지의 양극(상대전극 또는 대향전극)으로는 통상적으로 백금과 같은 물질이 사용되며 유리기판상에 제공된다. 음극과 상대전극이 합착된 사이에는 전해질이 제공되게 된다.The cathode of the dye-sensitized solar cell is composed of an oxide semiconductor film composed of a transparent conductive film formed on a glass substrate and oxide semiconductor nanoparticles such as TiO 2 . On the oxide semiconductor film, a dye polymer is provided by a method such as adsorption. As a positive electrode (counter electrode or counter electrode) of the dye-sensitized solar cell, a material such as platinum is generally used and provided on a glass substrate. An electrolyte is provided between the negative electrode and the counter electrode.
일반적인 염료감응 태양전지의 작동원리는 다음과 같다. 태양광이 전지에 입사하여 염료고분자를 여기시켜서 전자-홀 쌍을 형성하고, 생성된 전자가 반도체 산화물의 전도띠로 주입된다. 주입된 전자는 반도체 산화물을 지나 외부로 전달된다. 외부에 전기에너지를 전달한 전자는 상대전극에서 전해질의 산화/환원 반응에 의해 염료 고분자의 홀과 결합하게 된다.The general principle of dye-sensitized solar cell is as follows. Sunlight enters the cell to excite the dye polymer to form an electron-hole pair, and the generated electrons are injected into the conduction band of the semiconductor oxide. The injected electrons are transferred to the outside through the semiconductor oxide. The electrons that transfer electric energy to the outside are combined with the holes of the dye polymer by the oxidation / reduction reaction of the electrolyte at the counter electrode.
염료에 의한 광전현상에 관해서는 1887년 비엔나 대학의 모세르(Moser) 박사에 의해 보고된 이후 꾸준히 연구되어 왔으며, 현재는 1991년 에콜 폴리테크 페데랄(Ecole Polytechnique Federale)의 그라첼(Gratzel) 교수의 연구팀에 의해 보고된 Ru계 염료와 I-/I3 - 전해질을 사용한 11 % 대의 최고 효율을 지닌 통칭 그라첼(Gratzel) 전지가 주로 연구되고 있다.Dye photoelectric phenomena have been steadily studied since reported by Dr. Moser of the University of Vienna in 1887 and now by Professor Gratzel of Ecole Polytechnique Federale in 1991 of the Ru-based dye and I reported by researchers - / I 3 - is known as having a 11% range with the highest efficiency, an electrolyte that Rachel (Gratzel) battery has been mainly studied.
이와 같은 염료가 흡착되는 광전극은 많은 염료를 흡착하기 위해 비표면적이 높은 광전극을 사용하는 것이 필수적이다. 종래에는 광전극 물질로 TiO2가 주로 사용되고 있지만, 현재까지 최고 효율이 10%에 머물러 새로운 광전극 물질의 개발 필요성이 대두되고 있다. In the photoelectrode to which such dye is adsorbed, it is essential to use a photoelectrode having a high specific surface area in order to adsorb many dyes. Conventionally, TiO 2 is mainly used as a photoelectrode material, but until now, the highest efficiency remains at 10%, and a need for developing a new photoelectrode material is emerging.
상기한 기술적 과제를 달성하기 위하여 본 발명은 종래의 TiO2 막을 대체할 수 있는 Ba-Sn-O 기반의 신규한 다성분계 산화물 반도체막을 제공하는 것을 목적으로 한다.In order to achieve the above technical problem, an object of the present invention is to provide a novel multi-component oxide semiconductor film based on Ba—Sn—O that can replace the conventional TiO 2 film.
또한 본 발명은 종래에 비해 염료감응 태양전지의 광전 에너지 변환 효율이 증가된 Ba-Sn-O 기반의 신규한 다성분계 산화물 반도체막을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a novel Ba-Sn-O-based multi-component oxide semiconductor film with improved photoelectric energy conversion efficiency of the dye-sensitized solar cell compared to the prior art.
상기 기술적 과제를 달성하기 위하여 본 발명은 도전성 투명 기판; 및 상기 기판 상에 형성되는 하기 화학식으로 표시되는 다성분계 산화물 반도체막을 포함하는 염료감응 태양전지용 광전극을 제공한다.The present invention to achieve the above technical problem is a conductive transparent substrate; And it provides a dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
<화학식> <Formula>
BaSnO3 : M (여기서, M은 BaSnO3에 도핑되며, Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La 및 Rh로 이루어진 금속 원소 중 최소한 1종의 금속) BaSnO 3 : M where M is doped with BaSnO 3 , Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La And at least one metal of the metal element consisting of Rh)
상기 M은 Sr, Ca 및 Mg이고, 상기 BaSnO3의 결정 구조에서 Ba 자리의 최소한 일부를 치환하는 것일 수 있다. M may be Sr, Ca, and Mg, and may substitute at least a part of Ba sites in the crystal structure of BaSnO 3 .
또한, 상기 M은 Sb이고, 상기 BaSnO3의 결정 구조에서 Sn 자리의 최소한 일부를 치환하는 것일 수 있다. In addition, M is Sb, and may replace at least a part of the Sn site in the crystal structure of BaSnO 3 .
또한, 상기 M은 상기 BaSnO3의 밴드 구조에서 전도대를 상승시키는 금속일 수 있다. 이와 달리, 상기 M은 상기 BaSnO3의 전자 농도 또는 홀 농도를 증가시키는 금속일 수도 있다. In addition, M may be a metal that raises the conduction band in the band structure of BaSnO 3 . Alternatively, M may be a metal that increases the electron concentration or hole concentration of BaSnO 3 .
또한 상기 M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~5 at%로 포함된 것일 수 있다. In addition, M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content of the BaSnO 3 It may be included in 0.01 to 5 at% compared to Ba or Sn.
또한, 상기 M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~1 at%로 포함된 것일 수 있다.In addition, the M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content is BaSnO 3 It may be included in 0.01 to 1 at% of Ba or Sn.
또한, 본 발명은 상기 다성분계 산화물 반도체막 상에 염료가 흡착된 것을 특징으로 하는 염료감응 태양전지용 전극을 제공한다. In addition, the present invention provides a dye-sensitized solar cell electrode characterized in that the dye is adsorbed on the multi-component oxide semiconductor film.
또한, 상기 기술적 과제를 달성하기 위하여 본 발명은 도전성 투명 기판; 및 상기 기판 상에 형성되는 하기 화학식으로 표시되는 다성분계 산화물 반도체막을 포함하는 염료감응 태양전지용 광전극을 제공한다.In addition, the present invention to achieve the above technical problem is a conductive transparent substrate; And it provides a dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
<화학식> <Formula>
(Ba1-x, Srx)SnO3 (여기서, 0.05<x≤0.5)(Ba 1-x , Sr x ) SnO 3 , where 0.05 <x≤0.5
또한, 상기 기술적 과제를 달성하기 위하여 본 발명은, 도전성 투명 기판; 및 상기 기판 상에 형성되는 하기 화학식으로 표시되는 다성분계 산화물 반도체막을 포함하는 염료감응 태양전지용 광전극을 제공한다.In addition, the present invention to achieve the above technical problem, a conductive transparent substrate; And it provides a dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
<화학식> <Formula>
(Ba1-x, Srx)SnO3 : M (여기서, M은 Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 금속이고, 0.05<x≤0.5)(Ba 1-x , Sr x ) SnO 3 : M where M is Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh At least one metal selected from the group consisting of 0.05 <x ≦ 0.5)
상기 화학식에서 M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~5 at%로 포함된 것일 수 있다.In the above formula, M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc, and Rh, the content of which is BaSnO 3 It may be included in 0.01 to 5 at% of Ba or Sn.
또한, 상기 M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~1 at%로 포함된 것일 수 있다. In addition, the M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content is BaSnO 3 It may be included in 0.01 to 1 at% of Ba or Sn.
또한, 본 발명은 상기 다성분계 산화물 반도체막 상에 염료가 흡착된 것을 특징으로 하는 염료감응 태양전지용 전극을 제공한다. In addition, the present invention provides a dye-sensitized solar cell electrode characterized in that the dye is adsorbed on the multi-component oxide semiconductor film.
본 발명에 따르면, BaSnO3 반도체 산화막의 광전 에너지 변환 효율을 향상시켜 고효율의 태양전지 셀의 제조를 가능하는 광전극을 제공할 수 있게 된다. According to the present invention, the photoelectric energy conversion efficiency of the BaSnO 3 semiconductor oxide film can be improved to provide a photoelectrode capable of manufacturing a high efficiency solar cell.
도 1 본 발명의 바람직한 실시예에 따라 Sr 도핑된 BaSnO3 분말의 X선 회절 패턴을 분석한 그래프이다. 1 is a graph illustrating an X-ray diffraction pattern of Sr-doped BaSnO 3 powder according to a preferred embodiment of the present invention.
도 2는 도 1의 회절 패턴을 확대 도시한 그래프이다.FIG. 2 is an enlarged graph of the diffraction pattern of FIG. 1.
도 3은 본 발명의 바람직한 실시예에 따라 합성된 Sr 도핑 BaSnO3 분말의 UV 흡수율(Absorbance) 측정 결과를 나타낸 그래프이다.3 is a graph showing the results of UV Absorption (Absorbance) measurement of Sr-doped BaSnO 3 powder synthesized according to a preferred embodiment of the present invention.
도 4는 본 발명의 바람직한 실시예에 따라 합성된 Sr 도핑 BaSnO3 분말의 모트-쇼트키 분석(Mott Schottky Analysis) 결과를 나타낸 그래프이다.4 is a graph showing the results of Mott Schottky Analysis of Sr-doped BaSnO 3 powder synthesized according to a preferred embodiment of the present invention.
도 5는 본 발명의 바람직한 실시예에 따라 합성된 Sr 도핑 BaSnO3 분말의 전자현미경 사진이다.5 is an electron micrograph of a Sr-doped BaSnO 3 powder synthesized according to a preferred embodiment of the present invention.
도 6은 본 발명의 바람직한 실시예에 따른 태양전지 셀의 특성을 측정한 결과를 나타낸 그래프이다.6 is a graph showing the results of measuring the characteristics of the solar cell according to a preferred embodiment of the present invention.
도 7은 본 발명의 다른 실시예에 따라 합성된 태양전지 셀의 특성을 나타낸 그래프이다.7 is a graph showing the characteristics of the solar cell synthesized according to another embodiment of the present invention.
도 8은 다른 실시예에 따른 태양전지 셀의 특성을 측정한 결과를 나타낸 그래프이다.8 is a graph illustrating a result of measuring characteristics of a solar cell according to another embodiment.
도 9는 또 다른 실시예에 따른 태양전지 셀의 특성을 측정한 결과를 나타낸 그래프이다.9 is a graph showing the results of measuring the characteristics of the solar cell according to another embodiment.
이하 도면을 참조하여 본 발명의 바람직한 실시예를 설명함으로써 본 발명을 상술한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
본 발명은 하기 화학식 1로 표시되는 다성분계 산화물 반도체를 포함하는 광전극을 제공한다. The present invention provides a photoelectrode comprising a multi-component oxide semiconductor represented by the following formula (1).
<화학식 1> <Formula 1>
BaSnO3 : M (여기서, M은 BaSnO3에 도핑되며, Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La 및 Rh로 이루어진 금속 원소 중 최소한 1종의 금속)BaSnO 3 : M where M is doped with BaSnO 3 , Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La And at least one metal of the metal element consisting of Rh)
또한, 본 발명에서 화학식1의 금속 원소 M은 Ba 자리를 치환하거나 Sn 자리를 치환할 수 있다. 이 때, 도핑된 금속 원소들은 BaSnO3의 결정 구조를 유지하면서 밴드 구조를 변화시킨다. 보다 구체적으로는 도핑된 금속 원소들은 BaSnO3의 밴드 구조에서 전도대(conduction band)를 상승시켜, 태양전지의 셀 특성을 향상시킬 수 있게 된다. 예컨대, Sr, Ca 및 Mg은 Ba 자리를 치환하여 전도대를 향상시킬 수 있고, Sb는 Sn 자리를 치환하여 전도대를 향상시킬 수 있다. In addition, in the present invention, the metal element M of Chemical Formula 1 may substitute for Ba or Sn. At this time, the doped metal elements change the band structure while maintaining the crystal structure of BaSnO 3 . More specifically, the doped metal elements raise the conduction band in the band structure of BaSnO 3, thereby improving cell characteristics of the solar cell. For example, Sr, Ca, and Mg may improve the conduction band by substituting Ba sites, and Sb may improve the conduction band by substituting Sn sites.
또한, 도핑된 금속 원소들은 다른 메커니즘에 의해 태양전지의 셀 특성을 향상시킬 수 있다. 즉, 도핑된 금속 원소는 막 내의 전자 농도 및 홀 농도를 증가시켜 태양전지의 셀 특성을 향상시킨다. 예컨대, 도핑된 Zn, Pb, Ti, Mn, Sb, In, Zr, Te, Fe, Y, Sm, Sc, La 및 Rh은 전자 농도를 증가시키는 것을 주된 메커니즘으로 태양전지 셀 특성을 향상시킬 수 있다. 이와 달리, 도핑된 Co 및 K는 홀 농도를 증가시키는 것을 주된 메커니즘으로 태양전지 셀 특성을 향상시킬 수 있다. In addition, the doped metal elements may improve cell characteristics of the solar cell by other mechanisms. That is, the doped metal element increases the electron concentration and hole concentration in the film, thereby improving the cell characteristics of the solar cell. For example, doped Zn, Pb, Ti, Mn, Sb, In, Zr, Te, Fe, Y, Sm, Sc, La, and Rh can improve solar cell characteristics as the main mechanism for increasing electron concentration. . In contrast, doped Co and K may improve solar cell characteristics as the main mechanism for increasing hole concentration.
물론, 도핑 원소들에 의한 셀 특성 향상 메커니즘은 동시에 작동할 수도 있다.Of course, the cell characteristic enhancement mechanism by the doping elements may work at the same time.
후술하는 바와 같이, Sr 도핑의 경우 BaSnO3의 결정 구조 내에서 Ba을 치환하며, 결과적인 광전극의 반도체 산화막의 조성은 다음의 화학식2로 표현할 수 있다.As described later, in the case of Sr doping, Ba is substituted in the crystal structure of BaSnO 3 , and the resulting composition of the semiconductor oxide film of the photoelectrode may be represented by the following Chemical Formula 2.
<화학식 2><Formula 2>
(Ba1-x, Srx)SnO3 (Ba 1-x , Sr x ) SnO 3
유사하게 Ca, Mg, Zn 등의 금속 원소도 고용 한계 내에서 Ba 자리를 치환할 수 있으며, 위 화학식2는 일반적으로 다음의 화학식 3으로 표현될 수 있을 것이다.Similarly, metallic elements such as Ca, Mg, and Zn may also substitute Ba sites within the solid solution limit, and Chemical Formula 2 may be generally represented by the following Chemical Formula 3.
<화학식 3><Formula 3>
(Ba1-x, M1x)SnO3 (여기서, M1은 Sr, Ca 및 Mg로 이루어진 그룹 중에서 선택된 최소한 1종의 원소)(Ba 1-x , M1 x ) SnO 3 , where M1 is at least one element selected from the group consisting of Sr, Ca, and Mg
한편, BaSnO3 결정 구조 내의 Sn 자리를 다른 금속 원소가 치환할 수 있으며, 이 때에도 전술한 바와 같은 밴드 구조의 변화가 발생한다. On the other hand, another metal element can replace the Sn site in the BaSnO3 crystal structure, and at this time, the band structure change as described above occurs.
<화학식 4><Formula 4>
(Ba)(Sn1-y, M2y)O3 (Ba) (Sn 1-y , M2 y ) O 3
상기 M2로 기능하기 위한 도핑 원소로는 Sb가 선택될 수 있다. Sb may be selected as a doping element to function as M2.
또한, 이와 달리 본 발명에서 도핑되 금속 원소는 Ba이나 Sn 자리를 치환하는 것이 아니라 결정 구조 내부에 침입 고용될 수도 있다. Alternatively, the metal element doped in the present invention may not be substituted for Ba or Sn sites, but may invade into the crystal structure.
또한, 본 발명에서 전술한 도핑 가능한 금속 원소들은 1종 이상이 동시에 도핑될 수 있다.In addition, in the present invention, the above-described dopable metal elements may be doped at least one kind.
A. 액상법에 의한 BaSnO3 : M 분말의 제조A. Preparation of BaSnO 3 : M Powders by Liquid Phase Method
<제조예 1><Manufacture example 1>
SnCl4-5H2O와 BaCl2-2H2O, Sr(NO3)2를 원료 분말로 사용하였다. 혼합 분말의 조성이 (Ba+Sr) : Sn의 몰비를 1:1로 유지하면서, Sr : (Ba+Sr)의 몰비가 0~0.5 범위에서 변화하도록 각 원료 분말을 칭량하여 혼합하였다. 혼합된 분말을 30% 과산화수소수(물과 과산화수소 부피비 70:30)에 용해하여, 상기 혼합 용액에 pH가 9~11가 되도록 암모니아수를 투입하여 침전 반응시키고 12 시간 동안 숙성하였다. 이어서, 얻어진 침전물을 세척한 후 동결 건조하고, 건조된 분말을 900℃의 온도에서 약 2시간 어닐링하여 BaSnO3 : Sr 분말을 합성하였다. SnCl 4 -5H 2 O, BaCl 2 -2H 2 O, and Sr (NO 3 ) 2 were used as raw material powders. Each raw material powder was weighed and mixed so that the molar ratio of Sr: (Ba + Sr) changed in the range of 0 to 0.5, while maintaining the molar ratio of (Ba + Sr): Sn in a composition of 1: 1. The mixed powder was dissolved in 30% hydrogen peroxide water (70:30 volume ratio of water and hydrogen peroxide), ammonia water was added to the mixed solution so that the pH was 9-11, and precipitated and aged for 12 hours. Subsequently, the precipitate obtained was washed and then lyophilized, and the dried powder was annealed at a temperature of 900 ° C. for about 2 hours to synthesize BaSnO 3 : Sr powder.
도 1 본 발명의 바람직한 실시예에 따라 Sr 도핑된 BaSnO3 분말의 X선 회절 패턴을 분석한 그래프이다. 1 is a graph illustrating an X-ray diffraction pattern of Sr-doped BaSnO 3 powder according to a preferred embodiment of the present invention.
도 1을 참조하면, Sr이 Ba 대비 30 몰%까지 도핑되었음에도 불구하고 BaSnO3의 결정 구조를 잘 유지하고 있음을 보여준다. Referring to FIG. 1, it is shown that Sr maintains the crystal structure of BaSnO 3 well despite being doped to 30 mol% of Ba.
도 2는 도 1의 회절 패턴을 확대 도시한 그래프이다. 도면을 참조하면 Ba 첨가량에 따라 30.5도 부근의 회절 피크기 우측으로 쉬프트함을 알 수 있다. 이로부터 첨가된 Sr이 이차상의 형성 없이 BaSnO3 격자 구조 내에 온전히 고용되머, (Ba, Sr)SnO3를 형성함을 알 수 있다. FIG. 2 is an enlarged graph of the diffraction pattern of FIG. 1. Referring to the figure, it can be seen that the shift to the right side of the diffraction peak group near 30.5 degrees according to the amount of Ba added. It can be seen that the added Sr solidifies in the BaSnO 3 lattice structure without forming a secondary phase, thereby forming (Ba, Sr) SnO 3 .
도 3은 합성된 분말의 UV 흡수율(Absorbance) 측정 결과이고, 도 4는 모트-쇼트키 분석(Mott Schottky Analysis) 결과를 나타낸 그래프이다. UV 흡수율은 LAMBDA650(Perkinelmer)로 250~600 nm 영역에서 스캔하여 측정하였고, 모트 쇼트키는 Potentiostat(CHI 608C, CH Instrument)으로 1M KCl 전해질(pH 7)에서 작동 전극, 상대전극, 기준 전극의 3전극 시스템을 이용하여 측정하였다. FIG. 3 is a result of measuring UV absorption of the synthesized powder, and FIG. 4 is a graph showing a Mott Schottky Analysis result. UV absorption was measured by scanning in the 250-600 nm region with LAMBDA650 (Perkinelmer), and Mort Schottky measured 3 of the working electrode, counter electrode and reference electrode in 1M KCl electrolyte (pH 7) with Potentiostat (CHI 608C, CH Instrument). Measurement was made using an electrode system.
도 3을 참조하면, Sr의 도핑에 따라 밴드 갭이 증가하는 것을 확인할 수 있다. Referring to FIG. 3, it can be seen that the band gap increases with the doping of Sr.
또한 도 4로부터 Sr의 도핑에 따라 전도대(conduction band)가 상승한다는 것을 간접적으로 확인할 수 있는데, 즉 밴드갭의 증가는 전도대(conduction band) 상승에 의한 것이라는 것을 확인 할 수 있다. 결국, Sr 도핑은 BaSnO3의 밴드 구조를 바꾸어 태양전지의 Voc 및 FF 등의 특성을 증가시키게 될 것을 짐작할 수 있다. In addition, it can be confirmed indirectly that the conduction band rises according to the doping of Sr from FIG. 4, that is, the increase of the band gap is due to the rise of the conduction band. As a result, Sr doping may change the band structure of BaSnO 3 to increase the characteristics of the solar cell, such as Voc and FF.
도 5는 Sr이 도핑된 BaSnO3 분말의 전자현미경 사진이다. 도 3으로부터 Sr의 첨가에 따라 분말 입자의 형상이나 크기의 변화가 거의 없음을 알 수 있다. 따라서, 도핑에 따른 셀 효율 등의 특성에 분말의 형상이나 크기에 의한 효과는 무시할 수 있음을 알 수 있다. 5 is an electron micrograph of a Sr-doped BaSnO 3 powder. It can be seen from FIG. 3 that there is little change in shape or size of the powder particles with the addition of Sr. Therefore, it can be seen that the effect of the shape and size of the powder on the characteristics such as cell efficiency due to doping can be ignored.
<제조예 2> <Manufacture example 2>
제조예 1의 Sr 소스를 Ca(NO3)2-4H2O로 대체한 외에는 제조예 1과 동일한 조건으로 BaSnO3 : Ca 분말을 합성하였다. BaSnO 3 : Ca powder was synthesized under the same conditions as Preparation Example 1 except that the Sr source of Preparation Example 1 was replaced with Ca (NO 3 ) 2 -4H 2 O.
B. 고상법에 의한 BaSnO3 : M 분말의 제조B. Preparation of BaSnO 3 : M Powders by Solid Phase Method
<제조예 3><Manufacture example 3>
원료분말로 BaCO3, SnO2 및 MgCO3를 원료 분말로 사용하였다. 이 때, 혼합 분말의 조성이 (Ba+Mg) : Sn의 몰비를 1:1로 유지하면서, Mg : (Ba+Mg)의 몰비가 0~0.05 범위에서 변화하도록 각 원료 분말을 칭량하여 혼합하였다. 혼합 분말과 분산제(폴리카복실산, MALIALIM AFB-1521)를 에탄올 용매 내에서, 12시간 볼 밀링하여 혼합하였다. 혼합된 슬러리를 건조하고, 1100도의 대기 분위기에서 2 시간 열처리 하여 BaSnO3 : Mg 분말을 합성하였다. BaCO 3 , SnO 2 and MgCO 3 were used as raw powders. At this time, the composition powders were weighed and mixed so that the molar ratio of Mg: (Ba + Mg) varied from 0 to 0.05 while the molar ratio of (Ba + Mg): Sn was maintained at 1: 1. . The mixed powder and dispersant (polycarboxylic acid, MALIALIM AFB-1521) were mixed by ball milling in an ethanol solvent for 12 hours. The mixed slurry was dried and heat-treated for 2 hours in an air atmosphere of 1100 degrees to synthesize BaSnO 3 : Mg powder.
합성된 BaSnO3 : Mg 분말은 Mg의 도핑 농도(Ba+Mg에 대한 Mg의 몰비)가 낮은 도핑 농도에서는 1차 입자의 형상이 큐빅 형태를 나타내었으나, 도핑 농도가 증가하면서 1차 입자의 형상이 사라지면서 응집으로 인한 조대 입자의 생성이 두드러졌다.The synthesized BaSnO 3 : Mg powder showed the cubic form of the primary particles at low doping concentration (molar ratio of Mg to Ba + Mg), but the shape of the primary particles was increased as the doping concentration was increased. As it disappeared, the formation of coarse particles due to aggregation became prominent.
<제조예 4><Manufacture example 4>
원료분말로 MgCO3를 CaCO3로 대체한 것을 제외하고는 제조예 4와 동일한 조건에서 BaSnO3 : Ca 분말을 합성하였다.BaSnO 3 : Ca powder was synthesized under the same conditions as in Preparation Example 4, except that MgCO 3 was replaced with CaCO 3 as a raw material powder.
<제조예 5>Production Example 5
원료분말로 MgCO3를 SrCO3로 대체한 것을 제외하고는 제조예 4와 동일한 조건에서 BaSnO3 : Sr 분말을 합성하였다.BaSnO 3 : Sr powder was synthesized under the same conditions as in Preparation Example 4, except that MgCO 3 was replaced with SrCO 3 as a raw material powder.
<제조예 6><Manufacture example 6>
원료분말로 MgCO3를 ZnO 대체한 것을 제외하고는 제조예 4와 동일한 조건에서 BaSnO3 : Zn 분말을 합성하였다.BaSnO 3 : Zn powder was synthesized under the same conditions as in Preparation Example 4, except that MgCO 3 was replaced with ZnO as the starting powder.
합성된 BaSnO3 : Zn 분말은 Zn의 도핑 농도(Ba+Zn에 대한 Zn의 몰비)가 증가할수록 1차 입자의 형상이 변함을 확인하였다.The synthesized BaSnO 3 : Zn powder was confirmed that the shape of the primary particles changes as the doping concentration of Zn (molar ratio of Zn to Ba + Zn) increases.
<제조예 7><Manufacture example 7>
원료분말로 BaCO3, SnO2 및 Sb2O3를 원료 분말로 사용하였다. 이 때, 혼합 분말의 조성이 Ba : (Sn+Sb)의 몰비를 1:1로 유지하면서, Sb : (Sn+Sb)의 몰비가 0~0.05 범위에서 변화하도록 각 원료 분말을 칭량하여 혼합하였다. 밀링, 건조 및 열처리 조건은 제조예 4와 동일한 조건에서 수행하여, BaSnO3 : Sb 분말을 합성하였다. BaCO 3 , SnO 2 and Sb 2 O 3 were used as raw material powders. At this time, the composition of the mixed powder was weighed and mixed so that the molar ratio of Sb: (Sn + Sb) varied from 0 to 0.05 while the molar ratio of Ba: (Sn + Sb) was 1: 1. . Milling, drying and heat treatment conditions were carried out under the same conditions as in Preparation Example 4 to synthesize BaSnO 3: Sb powder.
C. 광전극의 제조C. Preparation of Photoelectrode
<실시예 1> <Example 1>
유기물인 터피놀(terpineol)과 에틸 셀룰로오스(ethyl cellulose)가 섞인 용액에, 앞서 제조예 1에 의해 제조된 BaSnO3 : Sr 분말을 혼합하여 페이스트를 형성하고 형성된 페이스트를 스크린 프린팅 방법으로 FTO 기판 상에 도포하였다. 이렇게 형성된 막의 유기물을 제거하기 위해 500℃에서 1시간 열처리를 하여 BaSnO3 : Sr 막을 형성한다. 형성된 막의 두께는 약 10~15 마이크로미터였다.BaSnO 3: Sr powder prepared by Preparation Example 1 was mixed with a solution of organic terpineol and ethyl cellulose to form a paste, and the formed paste was applied onto the FTO substrate by screen printing. It was. The BaSnO 3 : Sr film is formed by heat treatment at 500 ° C. for 1 hour to remove the organic material of the film thus formed. The thickness of the formed film was about 10-15 micrometers.
기판 상에 소정 두께의 BaSnO3 : Sr 막을 형성한 후, 제조된 막을 염료(루테늄 계열의 N719 dye (cis-diisothiocyanato-bis(2,2-bipyridyl-4,4-dicarboxylato) ruthenium(II) bis(tetrabutylammonium)를 에탄올에 0.05nM 농도로 용해한 용액)에 소정 시간 딥핑하여 염료를 흡착하였다. After the BaSnO 3 : Sr film having a predetermined thickness was formed on the substrate, the prepared film was subjected to dye (ruthenium-based N719 dye (cis-diisothiocyanato-bis (2,2-bipyridyl-4,4-dicarboxylato) ruthenium (II) bis ( The dye was adsorbed by dipping for a predetermined time in tetrabutylammonium) solution dissolved in ethanol at a concentration of 0.05 nM.
<실시예 2> <Example 2>
제조예 2에 의해 제조된 BaSnO3 : Ca 분말을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 BaSnO3 : Ca 막을 형성하고 염료를 흡착하였다. A BaSnO 3 : Ca film was formed in the same manner as in Example 1 except that BaSnO 3 : Ca powder prepared in Preparation Example 2 was used, and the dye was adsorbed.
<실시예 3><Example 3>
제조예 3에 의해 제조된 BaSnO3 : Mg 분말을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 BaSnO3 : Mg 막을 형성하고 염료를 흡착하였다. A BaSnO 3 : Mg film was formed in the same manner as in Example 1 except that BaSnO 3 : Mg powder prepared in Preparation Example 3 was used, and the dye was adsorbed.
<실시예 4> <Example 4>
제조예 4에 의해 제조된 BaSnO3 : Ca 분말을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 BaSnO3 : Ca 막을 형성하고 염료를 흡착하였다. A BaSnO 3 : Ca film was formed in the same manner as in Example 1 except that BaSnO 3 : Ca powder prepared in Preparation Example 4 was used, and the dye was adsorbed.
<실시예 5> Example 5
제조예 5에 의해 제조된 BaSnO3 : Sr 분말을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 BaSnO3 : Sr 막을 형성하고 염료를 흡착하였다. A BaSnO 3 : Sr film was formed in the same manner as in Example 1 except that BaSnO 3 : Sr powder prepared in Preparation Example 5 was used, and the dye was adsorbed.
<실시예 6><Example 6>
제조예 6에 의해 제조된 BaSnO3 : Zn 분말을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 BaSnO3 : Zn 막을 형성하고 염료를 흡착하였다. A BaSnO 3 : Zn film was formed in the same manner as in Example 1 except that BaSnO 3 : Zn powder prepared in Preparation Example 6 was used, and the dye was adsorbed.
<실시예 7> <Example 7>
제조예 7에 의해 제조된 BaSnO3 : Sb 분말을 사용한 점을 제외하고는 실시예 1과 동일한 방법으로 BaSnO3 : Sb 막을 형성하고 염료를 흡착하였다. A BaSnO 3 : Sb film was formed in the same manner as in Example 1 except that BaSnO 3 : Sb powder prepared in Preparation Example 7 was used, and the dye was adsorbed.
C. 광전극의 특성 평가C. Characterization of Photoelectrode
반도체막이 형성된 FTO 기판을 작동 전극으로 하여 염료감응 태양전지를 제작하였다. 이 때, 염료감응 태양전지의 양극(상대전극 또는 대향전극)은 스퍼터링법을 이용하여 Pt를 유리 기판상에 형성한 것을 사용하였고, 이렇게 형성된 상대전극과 BaSnO3막이 형성된 작동 전극을 샌드위치 타입의 형태로 패킹하여 셀을 제조한 후, 요오드 계열의 전해질을 사용하여 패킹된 셀에 주입하였다. The dye-sensitized solar cell was produced using the FTO board | substrate with which the semiconductor film was formed as a working electrode. At this time, the anode (relative electrode or counter electrode) of the dye-sensitized solar cell was formed by using Pt formed on the glass substrate by sputtering method, and the counter electrode and the working electrode on which the BaSnO 3 film was formed were sandwiched. After the cell was prepared by packing, it was injected into the packed cell using an iodine-based electrolyte.
제작된 염료감응 태양전지 셀의 I-V 특성을 측정하여, 전류밀도(Jsc), Voc, FF(fill factor), 전지 효율(Efficiency)을 구하였다.I-V characteristics of the fabricated dye-sensitized solar cell were measured to determine current density (Jsc), Voc, fill factor (FF), and battery efficiency.
도 6은 실시예 1의 Sr이 도핑된 광전극을 작동 전극으로 하여 측정한 태양전지 셀의 특성을 측정한 결과를 나타낸 그래프이다.6 is a graph showing the results of measuring the characteristics of the solar cell measured by using the Sr-doped photoelectrode of Example 1 as the working electrode.
먼저, 도 6의 (a)를 참조하면, Sr 도핑 농도가 0~20%까지 증가하면서 Jsc가 소폭 증가함을 알 수 있다. 또, 도 6의 (b)에 나타난 바와 같이, Sr 도핑 농도가 증가함에 따라 Voc가 증가하며 대략 도핑 농도 30%에서 최대치를 나타냄을 알 수 있다. 또한, 도 6의 (c)에 나타난 바와 같이 도핑 농도 5~20% 범위에서 Fill Factor가 양호한 값을 가짐을 알 수 있다. First, referring to FIG. 6 (a), it can be seen that the Jsc increases slightly while the Sr doping concentration is increased to 0-20%. In addition, as shown in (b) of FIG. 6, as the Sr doping concentration increases, it can be seen that Voc increases and shows a maximum at approximately 30% of the doping concentration. In addition, as shown in Figure 6 (c) it can be seen that the Fill Factor has a good value in the doping concentration of 5 ~ 20% range.
도 6의 (d)에 나타난 바와 같이, 전지 효율은 도핑 농도 5~20% 범위에서 가장 좋은 효율을 나타냄을 알 수 있다. As shown in Figure 6 (d), it can be seen that the battery efficiency shows the best efficiency in the doping concentration of 5 ~ 20% range.
아래 표 1은 Sr이 20% 도핑된 광전극으로 구성된 태양전지 셀(Sr20)과 도핑되지 않은 광전극으로 구성된 태양전지 셀(Bare1, Bare2)의 특성을 대비하여 도시한 표이다. Table 1 below is a table comparing the characteristics of the solar cell (Sr20) consisting of a photoelectrode doped with 20% Sr and the solar cells (Bare1, Bare2) consisting of an undoped photoelectrode.
표 1
구분 Jsc Voc FF Efficiency
Bare1 10.11 0.62 0.67 4.18
Bare1 10.23 0.62 0.67 4.22
Sr20 11.55 0.67 0.69 5.32
Table 1
division Jsc Voc FF Efficiency
Bare1 10.11 0.62 0.67 4.18
Bare1 10.23 0.62 0.67 4.22
Sr20 11.55 0.67 0.69 5.32
위 표에서 알 수 있는 바와 같이, Sr이 20% 도핑된 셀의 효율은 도핑되지 않은 셀에 비해 대략 26% 정도 증가함을 알 수 있다. As can be seen in the above table, the efficiency of the cell doped with 20% Sr is about 26% increase compared to the undoped cell.
한편, 태양전지 셀의 효율은 분말의 제조 방법이나 셀의 구성 등의 다른 요인에 영향을 받는데, 본 실시예는 고상 합성법에 의해 합성된 경우를 나타낸 것으로 효율의 절대값이 낮다. 그러나, 동일한 조건으로 제조된 도핑되지 않은 BaSnO3 광전극 셀과 대비하면 본 발명에 따라 제작된 광전극이 매우 높은 효율을 나타냄은 잘 알 수 있다.On the other hand, the efficiency of the solar cell is influenced by other factors such as the manufacturing method of the powder, the configuration of the cell, etc. The present embodiment shows a case of synthesis by the solid-phase synthesis method, the absolute value of the efficiency is low. However, it can be seen that the photoelectrode fabricated according to the present invention exhibits very high efficiency as compared to the undoped BaSnO 3 photoelectrode cell prepared under the same conditions.
도 7은 실시예 1에 비해 막 두께를 35~40 마이크로미터로 증가시켜 측정한 태양전지 셀의 특성을 나타낸 그래프이다. 도 7에서 알 수 있는 바와 같이, 막 두께의 증가에 따라 효율이 증가하였음을 알 수 있다. 7 is a graph showing the characteristics of the solar cell measured by increasing the film thickness to 35 ~ 40 micrometers compared to Example 1. As can be seen in Figure 7, it can be seen that the efficiency increased with the increase of the film thickness.
도 8은 실시예 2의 Ca가 도핑된 광전극을 작동 전극으로 하여 측정한 태양전지 셀의 특성을 측정한 결과를 나타낸 그래프이다.8 is a graph showing the results of measuring the characteristics of the solar cell measured by using the Ca-doped photoelectrode of Example 2 as the working electrode.
도 8에 도시된 바와 같이, 소량의 Ca 예컨대 Ca 농도 2~3%까지 Jsc가 증가함을 알 수 있다.As shown in FIG. 8, it can be seen that Jsc increases up to a small amount of Ca, such as Ca, from 2 to 3%.
위 그래프로부터 Ca 첨가의 경우 Ba 자리를 치환하여 BaSnO3 막의 밴드 구조를 바꾸고 태양전지 특성을 향상시키는 것을 알 수 있다. From the above graph, it can be seen that in the case of Ca addition, the Ba site is replaced to change the band structure of the BaSnO 3 film and improve the solar cell characteristics.
아래 표 2는 실시예 3 내지 6에 의해 제조된 광전극을 작동 전극으로 하여 측정한 태양전지 셀의 특성을 측정한 결과를 나타낸 표이다. 비교를 위해 도핑되지 않은 광전극으로 된 셀(Bare)의 특성 측정 결과를 함께 나타내었다.Table 2 below is a table showing the results of measuring the characteristics of the solar cell measured by using the photoelectrode prepared in Examples 3 to 6 as the working electrode. For comparison, the results of the measurement of the characteristics of a cell (bar) of an undoped photoelectrode are shown.
표 2
Figure PCTKR2013006811-appb-T000001
 TABLE 2
Figure PCTKR2013006811-appb-T000001
위 표로부터 전반적인 도핑 범위에서 향상된 효율을 나타냄을 알 수 있다. 모든 도핑 원소들은 1.0 at%의 도핑 농도 범위 내에서는 전반적인 셀 특성의 향상을 나타내고 있으며, Mg나 Ca의 경우 5.0 at%의 도핑 농도에서 전반적인 특성 향상 경향을 나타내고 있음을 알 수 있다. From the table above it can be seen that the improved efficiency in the overall doping range. All doping elements show an improvement in the overall cell characteristics in the doping concentration range of 1.0 at%, and it can be seen that Mg or Ca shows an overall improvement in the doping concentration at 5.0 at%.
한편, 실시예 3 내지 6은 고상법에 의해 제조된 분말을 사용한 것으로, 액상법에 의해 제조된 분말에 비해서는 상대적으로 낮은 효율을 보여주고 있다. On the other hand, Examples 3 to 6 are used by the powder produced by the solid-phase method, showing a relatively low efficiency compared to the powder produced by the liquid phase method.
도 9는 실시예 7에 의해 제조된 광전극으로 된 셀의 전류밀도를 측정한 결과를 나타낸 그래프이다. 9 is a graph showing the results of measuring the current density of the cell of the photoelectrode prepared in Example 7.
도 9로부터 Sb의 첨가에 의해서도 전류밀도의 증가 현상이 발생함을 알 수 있다. 즉 Sb 첨가량이 Sn 대비 0.1 at%인 경우 전류밀도의 증가 현상이 관찰되는데, 이 때 도핑된 Sb는 BaSnO3의 Sn 자리 일부를 치환하고 밴드 특성을 바꾸는 메커니즘에 의해 셀 특성을 향상시키는 것으로 이해될 수 있다. 물론, Sb 첨가에 따른 셀 특성의 향상은 다른 메커니즘, 즉 전자 농도나 홀 농도의 증가에 기인한 것일 수도 있다. It can be seen from FIG. 9 that the phenomenon of an increase in current density also occurs by addition of Sb. In other words, when the amount of Sb added is 0.1 at% compared to Sn, an increase in current density is observed. In this case, the doped Sb may be understood to improve cell characteristics by a mechanism of replacing a portion of Sn sites in BaSnO3 and changing band characteristics. have. Of course, the improvement of cell characteristics due to the addition of Sb may be due to other mechanisms, namely, an increase in electron concentration or hole concentration.
이상 본 발명의 바람직한 실시예를 상술하였지만, 이 실시예들은 본 발명을 한정하는 것이 아니다. 예컨대, 본 발명의 당업자라면 본 발명의 실시예로 언급되는 도핑 금속들 중 2 종 이상의 금속 원소가 동시에 도핑되는 경우에도 결과적인 전지의 특성이 향상될 것임은 누구나 알 수 있을 것이다. 또한, 이와 같은 2종 이상의 금속 원소는 BaSnO3의 결정 구조 내에서 Ba 자리와 Sn 자리를 모두 치환하는 원소들일 수도 있으며, 그 중 하나의 자리만 치환하는 금속 원소들일 수도 있다. 또한, 이들 금속 원소들은 결정 구조 내의 Ba 또는 Sn 자리를 치환하는 것이 아니라 격자 구조 내에 침입하여 고용되는 금속들일 수도 있을 것이다. Although the preferred embodiments of the present invention have been described above, these embodiments do not limit the present invention. For example, it will be appreciated by those skilled in the art that even when two or more metal elements of the doped metals mentioned in the embodiments of the present invention are doped simultaneously, the characteristics of the resulting battery will be improved. In addition, such two or more metal elements may be elements replacing both Ba and Sn sites in the crystal structure of BaSnO 3 , or may be metal elements replacing only one site thereof. In addition, these metal elements may be metals penetrating into the lattice structure rather than substituting Ba or Sn sites in the crystal structure.

Claims (13)

  1. 도전성 투명 기판; 및Conductive transparent substrates; And
    상기 기판 상에 형성되는 하기 화학식으로 표시되는 다성분계 산화물 반도체막을 포함하는 염료감응 태양전지용 광전극.Dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
    <화학식> <Formula>
    BaSnO3 : M (여기서, M은 BaSnO3에 도핑되며, Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, La, Co 및 Rh로 이루어진 금속 원소 중 최소한 1종의 금속)BaSnO 3 : M where M is doped with BaSnO 3 , Sr, Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, La, Co And at least one metal of the metal element consisting of Rh)
  2. 제1항에 있어서, The method of claim 1,
    M은 Sr, Ca 및 Mg로 이루어진 그룹 중에서 선택된 최소한 1종의 금속이고, M is at least one metal selected from the group consisting of Sr, Ca and Mg,
    상기 BaSnO3의 결정 구조에서 Ba 자리의 최소한 일부를 치환하는 것을 특징으로 하는 염료감응 태양전지용 전극.The electrode for a dye-sensitized solar cell, characterized in that to replace at least a portion of the Ba site in the crystal structure of BaSnO 3 .
  3. 제1항에 있어서, The method of claim 1,
    M은 Sb이고, M is Sb,
    상기 BaSnO3의 결정 구조에서 Sn 자리의 최소한 일부를 치환하는 것을 특징으로 하는 염료감응 태양전지용 전극.The electrode for a dye-sensitized solar cell, characterized in that to replace at least a portion of the Sn site in the crystal structure of BaSnO 3 .
  4. 제1항에 있어서, The method of claim 1,
    상기 M은 상기 BaSnO3의 밴드 구조에서 전도대를 상승시키는 금속인 것을 특징으로 하는 염료감응 태양전지용 전극.M is a dye-sensitized solar cell electrode, characterized in that the metal to raise the conduction band in the band structure of BaSnO 3 .
  5. 제1항에 있어서, The method of claim 1,
    상기 M은 상기 BaSnO3의 전자 농도 또는 홀 농도를 증가시키는 금속인 것을 특징으로 하는 염료감응 태양전지용 전극.M is a dye-sensitized solar cell electrode, characterized in that the metal to increase the electron concentration or hole concentration of the BaSnO 3 .
  6. 제1항에 있어서, The method of claim 1,
    M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc, La, Co 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~5 at%로 포함된 것을 특징으로 하는 염료감응 태양전지용 전극.M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc, La, Co and Rh, the content of which is BaSnO Dye-sensitized solar cell electrode, characterized in that contained in 0.01 to 5 at% compared to Ba or Sn of 3 .
  7. 제1항에 있어서, The method of claim 1,
    M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~1 at%로 포함된 것을 특징으로 하는 염료감응 태양전지용 전극.M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content of which is Ba or Ba of BaSnO 3 Dye-sensitized solar cell electrode, characterized in that contained in 0.01 ~ 1 at% compared to Sn.
  8. 제1항에 있어서, The method of claim 1,
    상기 다성분계 산화물 반도체막 상에 염료가 흡착된 것을 특징으로 하는 염료감응 태양전지용 전극.Dye-sensitized solar cell electrode, characterized in that the dye is adsorbed on the multi-component oxide semiconductor film.
  9. 도전성 투명 기판; 및Conductive transparent substrates; And
    상기 기판 상에 형성되는 하기 화학식으로 표시되는 다성분계 산화물 반도체막을 포함하는 염료감응 태양전지용 광전극.Dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
    <화학식> <Formula>
    (Ba1-x, Srx)SnO3 (여기서, 0.05<x≤0.5)(Ba 1-x , Sr x ) SnO 3 , where 0.05 <x≤0.5
  10. 도전성 투명 기판; 및Conductive transparent substrates; And
    상기 기판 상에 형성되는 하기 화학식으로 표시되는 다성분계 산화물 반도체막을 포함하는 염료감응 태양전지용 광전극.Dye-sensitized solar cell photoelectrode comprising a multi-component oxide semiconductor film represented by the following formula formed on the substrate.
    <화학식> <Formula>
    (Ba1-x, Srx)SnO3 : M (여기서, M은 Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, La 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 금속이고, 0.05<x≤0.5)(Ba 1-x , Sr x ) SnO 3 : M (where M is Ca, Mg, Zn, Pb, Ti, Mn, Sb, K, In, Zr, Te, Fe, Y, Sm, Sc, Co, At least one metal selected from the group consisting of La and Rh, and 0.05 <x ≦ 0.5)
  11. 제10항에 있어서, The method of claim 10,
    M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~5 at%로 포함된 것을 특징으로 하는 염료감응 태양전지용 전극.M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content of which is Ba or Ba of BaSnO 3 Dye-sensitized solar cell electrode, characterized in that contained in 0.01 ~ 5 at% compared to Sn.
  12. 제10항에 있어서, The method of claim 10,
    M은 Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc 및 Rh로 이루어진 그룹 중에서 선택된 최소한 1종의 원소이고, 그 함량은 상기 BaSnO3의 Ba 또는 Sn 대비 0.01~1 at%로 포함된 것을 특징으로 하는 염료감응 태양전지용 전극.M is at least one element selected from the group consisting of Mg, Zn, Pb, Ti, Mn, K, In, Zr, Te, Fe, Y, Sm, Sc and Rh, the content of which is Ba or Ba of BaSnO 3 Dye-sensitized solar cell electrode, characterized in that contained in 0.01 ~ 1 at% compared to Sn.
  13. 제10항에 있어서, The method of claim 10,
    상기 다성분계 산화물 반도체막 상에 염료가 흡착된 것을 특징으로 하는 염료감응 태양전지용 전극.Dye-sensitized solar cell electrode, characterized in that the dye is adsorbed on the multi-component oxide semiconductor film.
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