KR100462006B1 - SnO2/TiO2 coupled oxide semiconductor and dye-sensitized solar cell - Google Patents
SnO2/TiO2 coupled oxide semiconductor and dye-sensitized solar cell Download PDFInfo
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- KR100462006B1 KR100462006B1 KR10-2001-0021250A KR20010021250A KR100462006B1 KR 100462006 B1 KR100462006 B1 KR 100462006B1 KR 20010021250 A KR20010021250 A KR 20010021250A KR 100462006 B1 KR100462006 B1 KR 100462006B1
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 31
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 16
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims description 17
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- GMRXNXPWWJDYFJ-UHFFFAOYSA-N [Li].NC(N)=O Chemical compound [Li].NC(N)=O GMRXNXPWWJDYFJ-UHFFFAOYSA-N 0.000 description 1
- PYZCGZCQFOBQRC-UHFFFAOYSA-L [O-]C(C1=CC(C2=NC=CC(C([O-])=O)=C2)=NC=C1)=O.O.O.[Ru+2] Chemical compound [O-]C(C1=CC(C2=NC=CC(C([O-])=O)=C2)=NC=C1)=O.O.O.[Ru+2] PYZCGZCQFOBQRC-UHFFFAOYSA-L 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DBZJJPROPLPMSN-UHFFFAOYSA-N bromoeosin Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C(O)C(Br)=C1OC1=C(Br)C(O)=C(Br)C=C21 DBZJJPROPLPMSN-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
Classifications
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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
- H01L31/04—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
- 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
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
-
- 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
Abstract
전도성표면을 갖는 투명유리기판(ITO유리)위에 산화주석과 산화티타늄을 각각 코팅한 산화주석/산화티타늄(SnO2/TiO2) 이중산화물 반도체막과 그 반도체막 표면에 에오신 Y 및 RuL2(SCN)2색소를 흡착시킨 SnO2/TiO2산화물 반도체전극을 제조하였으며, 그 SnO2/TiO2산화물 반도체전극과 그 대극 그리고 산화환원 전해질로 구성된 색소증감태양전지이다. SnO2/TiO2산화물 반도체막은 다공질구조를 갖으며, 그 산화물반도체막의 두께는 7 - 14.5㎛이며 그 산화물반도체 입자크기는 50nm 이하이다.Tin oxide / titanium oxide (SnO 2 / TiO 2 ) bioxide semiconductor film coated with tin oxide and titanium oxide on a transparent glass substrate (ITO glass) having a conductive surface, respectively, and Eosin Y and RuL 2 (SCN) on the surface of the semiconductor film. 2 ) A SnO 2 / TiO 2 oxide semiconductor electrode adsorbed with 2 dyes was fabricated, and is a dye-sensitized solar cell composed of the SnO 2 / TiO 2 oxide semiconductor electrode, a counter electrode, and a redox electrolyte. The SnO 2 / TiO 2 oxide semiconductor film has a porous structure, and the oxide semiconductor film has a thickness of 7-14.5 µm and an oxide semiconductor particle size of 50 nm or less.
Description
본 발명은 산화주석/산화티타늄(SnO2/TiO2) 이중산화물반도체전극과 그를 이용한 색소증감태양전지에 관한 것이다.The present invention relates to a tin oxide / titanium oxide (SnO 2 / TiO 2 ) double oxide semiconductor electrode and a dye-sensitized solar cell using the same.
종래의 태양전지는 주로 단결정, 다결정, 아몰퍼스 실리콘의 p-n접합을 이용하였다. 그러나 그 실리콘은 고순도를 필요로 하기 때문에 원료실리콘 정제과정이 필요로 하므로 생산단가가 높다. 따라서 저가격의 태양전지의 생산이 요구된다. 또한 Nature, vol.261 1976 p.402를 보면 산화아연분말을 압축성형한 소결체디스크 표면에 로즈베갈(rose begal)색소를 흡착시켜 제조한 산화물반도체를 이용한 색소증감태양전지가 제안되었다. 그 태양전지의 전압/전류곡선을 보면 0.2V의 기전압시의 전류값은 약 0.2 ㎂ 정도로 상당히 낮으므로 실용화하기는 불가능하다. 따라서 저가격, 고효율의 태양전지를 생산하기 위하여 SnO2/TiO2이중산화물반도체전극을 이용한 색소증감태양전지의 개발이 요구되어졌다.Conventional solar cells mainly use pn junctions of single crystals, polycrystals, and amorphous silicon. However, since the silicon requires high purity, the raw material silicon purification process is required, so the production cost is high. Therefore, production of low cost solar cells is required. In addition, according to Nature, vol.261 1976 p.402, a dye-sensitized solar cell using an oxide semiconductor prepared by adsorbing rose begal pigment on the surface of a sintered compact disc of zinc oxide powder is proposed. Looking at the voltage / current curve of the solar cell, the current value at a voltage of 0.2 V is considerably low, about 0.2 mA, which makes it practical. Therefore, development of dye-sensitized solar cells using SnO 2 / TiO 2 double oxide semiconductor electrodes has been required to produce low cost and high efficiency solar cells.
본 발명은 위와 같은 종래의 문제점을 해결하고자 하는 목적으로 안출되었으며, 이 문제를 해결하기 위해 여러 가지 실험을 행한 후 우선 한표면이 전도성을 갖는 투명유리기판에 산화주석을 코팅하고 그 위에 산화티탄을 코팅하여 SnO2/TiO2산화물반도체막을 형성시킨 후 색소(에오신 Y 및 RuL2(SCN)2)를 흡착시킨 SnO2/TiO2산화물반도체전극을 제조하였으며, 그 SnO2/TiO2산화물반도체전극과 그 대극 그리고 산화환원전해질로 구성된 색소증감태양전지의 개발에 성공하였다. 본 발명은 저가격이며 실용성있는 태양전지를 제공하는 것을 과제로 하고 있다.The present invention has been devised for the purpose of solving the conventional problems as described above, and after performing various experiments to solve this problem, first of all, the surface is coated with tin oxide on a transparent glass substrate having conductivity and titanium oxide thereon After coating to form a SnO 2 / TiO 2 oxide semiconductor film, a SnO 2 / TiO 2 oxide semiconductor electrode adsorbed with dyes (Eosin Y and RuL 2 (SCN) 2 ) was prepared, and the SnO 2 / TiO 2 oxide semiconductor electrode We have succeeded in developing a dye-sensitized solar cell composed of a counter electrode and a redox electrolyte. An object of the present invention is to provide a solar cell with low cost and practicality.
본 발명의 SnO2/TiO2산화물반도체전극 및 그 색소증감 태양전지는 다른 에너지준위를 갖는 두 산화물반도체를 이용하여 두층의 다른 다공질 산화물 반도체막으로 이루어져 있기 때문에 태양광을 조사할 때, 색소는 넓은 영역의 가시광을 흡수하여 전자는 여기되고 그 여기된 전자는 산화티타늄으로부터 산화주석에 순차적으로, 빠르게 운송됨으로써 전자와 홀(hole)의 재결합을 방지하게 되어 높은 효율을 가져온다. 그 산화물반도체는 나노입자로 평균입경은 50nm 이하이고 비표면적은 67㎡/g 이다.Since the SnO 2 / TiO 2 oxide semiconductor electrode and the dye-sensitized solar cell of the present invention are made of two different porous oxide semiconductor films using two oxide semiconductors having different energy levels, the pigment is wide when irradiated with sunlight. Electrons are excited by absorbing visible light in the region, and the excited electrons are sequentially transported rapidly from titanium oxide to tin oxide, thereby preventing recombination of electrons and holes, resulting in high efficiency. The oxide semiconductor is a nanoparticle with an average particle diameter of 50 nm or less and a specific surface area of 67 m 2 / g.
본 발명에 이용된 색소는 에오신 Y 및 RuL2(SCN)2색소이다. 에오신 Y(Eosin Y)색소는 2',4',5',7'-tetrabromofluorescein의 약자로서 최대 광 흡수파장은 524nm이다. RuL2(SCN)2색소는 cis-di(thiocyanato)-N,N'-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(Ⅱ) dihydrate의 약자로서 최대 광 흡수파장은 540nm이다. 두 색소의 최대 광 흡수영역은 모두 가시광 영역이며 카복실(carboxyl)기를 갖고 있다. 상기 두 색소를 선택하여 흡착시킨 목적은 색소의 카복실(carboxyl)기와 산화물 입자간의 에스테르 결합(ester linkage)에 의해 산화물반도체 표면에 색소가 잘 흡착되며, 그 색소흡착에 의해 산화물반도체의 광 흡수영역을 보다 장파장쪽으로 확장시킴으로서 넓은 가시광 영역(400∼700 nm)의 태양광을 흡수하기 위함이다. 한편, 산화물반도체에 색소를 흡착시키지 않은 전극의 경우 전체 태양광의 4%에 해당하는 400nm이하의 자외선만이 흡수될 뿐이다.The pigments used in the present invention are Eosin Y and RuL 2 (SCN) 2 pigments. Eosin Y is an abbreviation for 2 ', 4', 5 ', 7'-tetrabromofluorescein, with a maximum light absorption wavelength of 524 nm. RuL 2 (SCN) 2 pigment is an abbreviation for cis-di (thiocyanato) -N, N'-bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) -ruthenium (II) dihydrate. Is 540 nm. The maximum light absorption region of both pigments is visible light region and has a carboxyl group. The purpose of selecting and adsorbing the two pigments is that the dye is well adsorbed on the surface of the oxide semiconductor by ester linkage between the carboxyl group and the oxide particles of the pigment, and the light absorption region of the oxide semiconductor is absorbed by the dye adsorption. It is intended to absorb sunlight in a wide visible light region (400-700 nm) by extending toward longer wavelengths. On the other hand, in the case of the electrode which does not adsorb the dye on the oxide semiconductor, only ultraviolet rays of 400 nm or less, which corresponds to 4% of the total solar light, are absorbed.
본 발명의 SnO2/TiO2산화물 반도체 전극을 제조하기 위해 나노입자를 갖는 콜로이드 용액을 제조하였다. 그 콜로이드용액은 필요에 따라 물, 유기용매, 점도조절제 및 분산제를 첨가하여 도포액으로 이용하였다. 용매중에 산화물 반도체 나노입자농도는 5 ∼ 15 중량%이다.In order to manufacture the SnO 2 / TiO 2 oxide semiconductor electrode of the present invention, a colloidal solution having nanoparticles was prepared. The colloidal solution was used as a coating solution by adding water, an organic solvent, a viscosity modifier and a dispersant as necessary. The concentration of the oxide semiconductor nanoparticles in the solvent is 5 to 15% by weight.
다음으로 그 도포액을 전도성 표면을 갖는 투명유리기판 위에 도포, 건조, 공기중에서 소성하여 기판위에 산화물 반도체막을 형성하였다. 그 기판은 유리위에 ln2O3와 SnO2의 도전성 산화물막을 코팅한 ITO 유리를 이용하였다. 산화물 반도체막을 형성하기 위해 100℃에서 1시간 건조 후 500℃에서 30분 소성하였으며, 그 소성된 산화물 반도체막은 다공질 구조막으로서 그 표면의 비표면적은 67㎡/g이다.Next, the coating liquid was applied onto a transparent glass substrate having a conductive surface, dried, and fired in air to form an oxide semiconductor film on the substrate. The substrate was made of ITO glass coated with a conductive oxide film of ln 2 O 3 and SnO 2 on the glass. In order to form an oxide semiconductor film, it dried at 100 degreeC for 1 hour, and baked at 500 degreeC for 30 minutes. The baked oxide semiconductor film is a porous structure film, and the specific surface area of the surface is 67 m <2> / g.
다음으로 산화물 반도체막 표면에 색소를 단분자막으로서 흡착시켰다. 색소를 유기용매에 용해해서 얻어진 색소 용액중에 산화물 반도체막을 침적해서 80℃에서 30분∼1시간 동안 환류하여 색소흡착처리를 하였다. 그 막을 색소 용액에 침적하기 전에 다공질 구조막으로 인한 기포를 제거하기 위해 소성 후 냉각시 80℃에 도달하였을 때 꺼내어 아르곤가스로 산화물막중에 포함되어 있는 기포를 제거하였다. 용액중의 색소의 농도는 3∼3.2x10-4M이다.Next, the pigment | dye was made to adsorb | suck as a monomolecular film on the oxide semiconductor film surface. An oxide semiconductor film was immersed in a dye solution obtained by dissolving a dye in an organic solvent and refluxed at 80 ° C. for 30 minutes to 1 hour to perform a dye adsorption treatment. In order to remove the air bubbles caused by the porous structure film before the film was immersed in the dye solution, it was taken out after cooling and reached 80 ° C. to remove the air bubbles contained in the oxide film with argon gas. The density | concentration of the pigment in a solution is 3-3.2x10 <-4> M.
본 발명의 태양전지는 상기 ITO유리, SnO2/TiO2이중 산화물 반도체 전극, 산화환원(Redox) 전해질, 대극으로 구성되어 있다. 산화환원 전해질은 I―/I3 ―계의 전해질로서 아세트니트릴 속에 0.03M I2와 0.3M LiI로 용해된 용액이다. 대극은 백금전극 및 전도성 표면을 갖는 유리기판에 백금을 증착하여 사용하였다.The solar cell of the present invention comprises the ITO glass, SnO 2 / TiO 2 double oxide semiconductor electrode, a redox electrolyte, and a counter electrode. A solution dissolved in 2 0.03MI with 0.3M LiI in acetonitrile as the electrolyte of the system - the redox electrolyte is I - / I 3. The counter electrode was used by depositing platinum on a glass substrate having a platinum electrode and a conductive surface.
본 발명의 색소증감 태양전지는 상기 ITO유리, SnO2/TiO2산화물 반도체 전극, 전해질 및 대극으로 구성된 전체를 수지로 밀봉하였다. 그 산화물 반도체 전극에는 광을 조사할 수 있도록 설계하였다. 이러한 구조의 전지는 SnO2/TiO2산화물 반도체 전극에 크세논 램프의 가시광을 조사함으로써 산화물 반도체와 산화환원 전해질간의 전위차가 발생하고 양 전극간에 전류가 발생한다. 또한 가시광을 조사함으로서 광을 전기로의 변환하는 광전변환율 (IPCE, incident photon-to-current conversion efficiency)을 측정하였다.In the dye-sensitized solar cell of the present invention, the whole composed of the ITO glass, the SnO 2 / TiO 2 oxide semiconductor electrode, the electrolyte, and the counter electrode was sealed with a resin. The oxide semiconductor electrode was designed so that light could be irradiated. The battery having such a structure generates a potential difference between the oxide semiconductor and the redox electrolyte by irradiating visible light of a xenon lamp to the SnO 2 / TiO 2 oxide semiconductor electrode and generates a current between both electrodes. In addition, incident photon-to-current conversion efficiency (IPCE) for converting light into electricity was measured by irradiating visible light.
상세한 실시 예Detailed embodiment
제작한 전지는 그 전극면적이 각각 1x1cm와Φ0.7cm이다. 전지를 작동하는 광원은 500W의 크세논 램프를 이용하였으며 400nm 이하의 파장의 광은 카트시켰다. 단락전류 및 개방전압 그리고 광전변환율(IPCE)을 측정하였다. 산화물 반도체막은 가수분해(TiO2의 경우 해교, 수열처리 추가)하여 조제된 TiO2졸과 SnO2졸을 이용하여 도포, 건조, 소성하여 얻었다. 색소는 에오신 Y(EosinY) 및 RuL2(SCN)2를 이용하였다.The fabricated cells had an electrode area of 1 × 1 cm and Φ 0.7 cm, respectively. The light source for operating the cell was a 500 W xenon lamp, and the light of the wavelength below 400 nm was carted. The short-circuit current, open voltage and photoelectric conversion factor (IPCE) were measured. An oxide semiconductor film of hydrolysis (in the case of TiO 2 peptizing, hydrothermal treatment added) by using a preparation of TiO 2 and SnO 2 sol sol coating, drying, and firing to obtain. As the pigment, Eosin Y (EosinY) and RuL 2 (SCN) 2 were used.
SnO2/TiO2산화물반도체전극은 아래와 같이 제조하였다. 조제된 산화주석졸과 산화티타늄졸에 물, 유기용매, 점도 조절제 및 분산제를 첨가한 도포액을 조제하였으며, 그 도포액을 전도성유리기판(ITO) 위에 도포, 건조하여 500℃에서 30분 공기중에서 소성하였다. 그 막의 두께는 산화주석 3.5 ㎛이며 산화티타늄은 3.5에서 11 ㎛이다. 그 산화물막을 전도성유리기판과 함께 색소 용액 중에 침적해서 80℃에서 30분∼1시간동안 색소흡착처리를 행한 후 실온에서 건조하였다. 용액중의 색소의 농도는 3∼3.2x10-4M이었다. 에오신 Y 및 RuL2(SCN)2색소 모두 SnO2/TiO2산화물반도체 표면에 잘 흡착되었다.SnO 2 / TiO 2 oxide semiconductor electrode was prepared as follows. To the prepared tin oxide sol and titanium oxide sol was added a coating solution containing water, an organic solvent, a viscosity modifier and a dispersing agent. The coating solution was applied on a conductive glass substrate (ITO), dried and air-dried at 500 ° C. for 30 minutes in air. Fired. The thickness of the film is 3.5 [mu] m of tin oxide and titanium oxide is 3.5 to 11 [mu] m. The oxide film was deposited with a conductive glass substrate in a dye solution, subjected to a dye adsorption treatment at 80 ° C. for 30 minutes to 1 hour, and then dried at room temperature. The density | concentration of the pigment in solution was 3-3.2x10 <-4> M. Both Eosin Y and RuL 2 (SCN) 2 pigments adsorbed well on the SnO 2 / TiO 2 oxide semiconductor surface.
위와 같이 색소가 흡착된 SnO2/TiO2산화물반도체전극과 대극을 전해질액에 접촉시켜 태양전지를 구성하였다. 그 경우 대극은 전도성유리에 백금을 30 nm두께로 증착하여 이용하였다. 색소가 흡착된 이중산화물반도체전극과 대극사이의 거리는 1 mm로 하였다. 전해질용액은 0.03 M I2(요소)와 0.3 M LiI(리튬요소)을 함유한 아세트니트릴 혼합액을 이용하였다. 이러한 색소증감태양전지에 있어서 SnO2/TiO2산화물반도체의 두께 및 색소에 따른 광전변환율(IPCE), 단락전류 및 개방전압은 다음과 같다. 에오신 Y 색소를 흡착시킨 3.5㎛ SnO2/3.5㎛ TiO2전극의 IPCE는 36.32％이고, 3.5㎛ SnO2/7㎛ TiO2/에오신 Y의 IPCE는 62.12％이고, 3.5㎛ SnO2/11㎛ TiO2/에오신 Y의 IPCE는 32.23％이다. 또한, RuL2(SCN)2색소를 흡착시킨 3.5㎛ SnO2/3.5㎛ TiO2전극의 IPCE는 74.35％이고, 3.5㎛ SnO2/7㎛ TiO2/RuL2(SCN)2의 IPCE, 단락전류, 개방전압은 88.1％, 4.72mA, 0.62V이다. 에오신 Y 색소와 비교하여 RuL2(SCN)2색소를 흡착시킨 전극이 보다 높은 광전변환율 (IPCE)을 나타내었으며, 3.5㎛ 두께의 SnO2와 7㎛ 두께의 TiO2를 갖는 이중산화물반도체 전극의 경우 최대 광전변환율을 나타내었다.The solar cell was constructed by contacting the dye-adsorbed SnO 2 / TiO 2 oxide semiconductor electrode and the counter electrode with the electrolyte solution. In this case, the counter electrode was used by depositing platinum to conductive glass at a thickness of 30 nm. The distance between the dye-adsorbed double oxide semiconductor electrode and the counter electrode was 1 mm. As the electrolyte solution, a mixed solution of acetonitrile containing 0.03 MI 2 (urea) and 0.3 M LiI (lithium urea) was used. In the dye-sensitized solar cell, the photoelectric conversion factor (IPCE), short circuit current, and open voltage according to the thickness and pigment of the SnO 2 / TiO 2 oxide semiconductor are as follows. IPCE of 3.5㎛ SnO 2 /3.5㎛ TiO 2 electrode adsorbing the dye Eosin Y is 36.32%, and, 3.5㎛ SnO 2 / 7㎛ IPCE is 62.12% of TiO 2 / eosin Y, 3.5㎛ SnO 2 / TiO 11㎛ IPCE of 2 / eosin Y is 32.23%. Also, RuL 2 (SCN) 3.5㎛ SnO IPCE of 2 /3.5㎛ TiO 2 electrode adsorbing the second pigment is 74.35%, 3.5㎛ SnO 2 / 7㎛ TiO 2 / RuL 2 (SCN) 2 in the IPCE, short-circuit current The open voltage is 88.1%, 4.72mA, 0.62V. Compared to the Eosin Y dye, the electrode adsorbed RuL 2 (SCN) 2 dye showed higher photoelectric conversion rate (IPCE), and in the case of the double oxide semiconductor electrode having 3.5 μm thick SnO 2 and 7 μm thick TiO 2 The maximum photoelectric conversion rate is shown.
본 발명의 색소증감태양전지는 다른 에너지준위를 갖는 산화주석과 산화티타늄의 산화물반도체로 구성된 이중구조를 갖고 있기 때문에 색소로부터 산화티타늄, 산화티타늄으로부터 산화주석으로 빠른 전자운송에 기인하여 전하의 재결합을 최대한 줄일 수 있기 때문에 높은 전지성능을 갖는다. 이중구조의 산화물 반도체 표면에 에오신 Y 및 RuL2(SCN)2색소를 흡착시킴으로서 넓은 가시광영역의 태양광을 흡수할 수 있었다. 본 발명의 색소증감 태양전지는 저가의 산화물반도체 분말로 제조되어지기 때문에 기존의 실리콘태양전지와 비교하여 1/3의 저가로 태양전지를 생산할 수 있다.Since the dye-sensitized solar cell of the present invention has a dual structure composed of tin oxide having a different energy level and an oxide semiconductor of titanium oxide, charge recombination is caused due to rapid electron transport from dye to titanium oxide and titanium oxide to tin oxide. High battery performance because it can be reduced as much as possible. By adsorbing Eosin Y and RuL 2 (SCN) 2 pigments on the surface of the double oxide semiconductor, sunlight in a wide visible region could be absorbed. Since the dye-sensitized solar cell of the present invention is made of a low-cost oxide semiconductor powder, it is possible to produce a solar cell at a third lower cost than conventional silicon solar cells.
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| JP2001076776A (en) * | 1999-09-09 | 2001-03-23 | Tdk Corp | Pigment-sensitized type solar cell |
| EP1282189A1 (en) * | 2000-04-12 | 2003-02-05 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Semiconductor layer, solar cell using it, and production methods and applications therefor |
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| JP2001076776A (en) * | 1999-09-09 | 2001-03-23 | Tdk Corp | Pigment-sensitized type solar cell |
| EP1282189A1 (en) * | 2000-04-12 | 2003-02-05 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | Semiconductor layer, solar cell using it, and production methods and applications therefor |
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