WO2013066023A1 - Highly efficient photoelectric device sensitized to an inorganic/organic heterojunction, inorganic semiconductor, and method for manufacturing same - Google Patents

Highly efficient photoelectric device sensitized to an inorganic/organic heterojunction, inorganic semiconductor, and method for manufacturing same Download PDF

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WO2013066023A1
WO2013066023A1 PCT/KR2012/008988 KR2012008988W WO2013066023A1 WO 2013066023 A1 WO2013066023 A1 WO 2013066023A1 KR 2012008988 W KR2012008988 W KR 2012008988W WO 2013066023 A1 WO2013066023 A1 WO 2013066023A1
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electron
oxide
light
hole
layer
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French (fr)
Korean (ko)
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석상일
임상혁
장정아
이용희
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한국화학연구원
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • 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
    • H01L31/18—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
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • 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
    • Y02E10/549—Organic PV 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 providing an inorganic semiconductor nanoparticle-sensitized photoelectric device having a high efficiency organic / organic heterojunction structure and a method of manufacturing the same.
  • a hole conductive polymer having the ability to absorb light in the wavelength band in the near infrared region in visible light and the ability to conduct holes in the light absorbing layer
  • a new structure of a photovoltaic cell having a novel structure in which an electron channel is formed in the hole conducting layer to easily separate electrons and holes to further increase light conversion efficiency
  • a method for producing the same In the case of generating excitons, which are electron-hole pairs, by absorbing light that has not been absorbed, a new structure of a photovoltaic cell having a novel structure in which an electron channel is formed in the hole conducting layer to easily separate electrons and holes to further increase light conversion efficiency And a method for producing the same.
  • dye molecules adsorbed on the surface of the porous photoanode generate electron-hole pairs by absorption of solar light, and electrons are injected into the conduction band of the semiconductor oxide used as the porous photoanode and transferred to the transparent electrode. To generate a current.
  • the oxidized dye molecules are reduced again by the oxidation-reduction pair of the electrolyte and the oxidized oxidation-reduction pair is transferred to the photocathode, whereby the solar cell operates.
  • this type of solar cell has a problem of sealing (sealing) by the use of a liquid electrolyte and problems of efficiency and stability of the artificially synthesized organic dye. Therefore, much research is being conducted on so-called inorganic semiconductor nanoparticle solar cells or quantum dot-sensitized solar cells which manufacture light absorption layers using inorganic semiconductor nanoparticles as light absorbers instead of dyes.
  • Inorganic semiconductor nanoparticle solar cells have a higher light absorption coefficient than conventional dye-sensitized solar cells, easy to control bandgap through nanoparticle size control, and high dipole moment. The separation of the resulting excitons into electron-holes is relatively easy.
  • Such inorganic semiconductor nanoparticles include chalcogenides such as PbSe, PbS, PbTe, CdS, CdSe, CdTe, Sb 2 S 3 , Sb 2 Se 3 , Cu 2 S and HgTe.
  • the chalcogenide-based inorganic semiconductor nanoparticles are attached to the porous electron transporter surface forming the electron transport layer used as the photoanode, thereby generating electron-hole (hole) pairs by external light.
  • the inorganic semiconductor nanoparticle light absorber conduction band should be higher than the conduction band of the electron transporter. The higher, the better the photoelectrons generated by the light is injected into the electron transporter.
  • the valence band of the hole conductor forming the hole conductive layer must be higher than that of the inorganic semiconductor nanoparticle light absorber. do.
  • the hole conductor itself should have a large band gap so as not to absorb light in the region absorbed by the inorganic semiconductor nanoparticle light absorber. If the band gap is small and the light absorber absorbs the light to be absorbed, the light absorbed by the light absorber is reduced, resulting in a decrease in efficiency.
  • An object of the present invention is to separate electrons and holes by forming an electron channel inside the hole conductive layer even when the hole conductive polymer used as the hole conductor of the hole conductive layer absorbs light in the inorganic semiconductor sensitive solar cell.
  • the present invention provides a method of manufacturing an optoelectronic device that maintains excellent photoelectric characteristics.
  • the present invention allows electrons and holes to be separated by forming electron channels inside the hole conductive layer even when the long wavelength light in the near infrared region, which is not absorbed by the semiconductor nanoparticle light absorbing layer, is additionally absorbed by the hole conductive layer. It is to provide a method for manufacturing an optoelectronic device that maintains excellent characteristics.
  • the photoelectric device As a result of much research in order to achieve the above object, the photoelectric device according to the present invention, an electron transport layer, a light absorbing layer of inorganic semiconductor nanoparticles attached to the surface of the electron transporter (electron transporter) constituting the electron transport layer and Comprising a hole conductive layer, the hole conductive layer includes a hole conductor for transmitting holes (holes) generated in the light absorption layer and an electron channel forming material for transmitting electrons by forming an electron channel in the hole conductive layer. It is.
  • the electron transporter constituting the electron transport layer is a porous metal oxide (photoanode electron transporter) capable of attaching a large amount of light-absorbing nano-inorganic semiconductor particles (light absorber, sensitizer) to the surface while transferring electrons.
  • the light absorbing layer refers to a layer made of a light absorbing body adsorbed on the surface of the electron transporting body.
  • the optoelectronic device has a large bandgap and transmits electrons and a light having a broad wavelength band of an electron transport layer of a porous metal oxide (photocathode electron transporter) capable of attaching a large amount of light-absorbing nano inorganic semiconductor particles to a surface thereof.
  • a light absorbing layer and a hole conducting layer which are light absorbers made of inorganic semiconductor nanoparticles that receive electrons and form holes (holes), wherein the hole conducting layer transfers holes generated in the light absorbing layer, and hole conduction.
  • An electron channel forming material is formed to form an electron channel inside the layer to absorb the light in the hole conducting layer and transfer the generated electrons.
  • the hole conductive polymer uses a material having a very large band gap so as not to absorb light in the wavelength band absorbed by the light absorber, the hole conductor having such characteristics is very limited and thus the selection thereof is limited. There is a problem that the use of the material constituting the device is limited.
  • a hole conductive polymer which is a hole conductive agent, even when the hole conductive polymer used as the hole conductor absorbs light in a region absorbed by the light absorption layer, It is possible to provide a new optoelectronic device and a method of manufacturing the same, which eliminates or minimizes the so-called filter effect that causes efficiency deterioration.
  • the present invention is to separate the electrons and holes in the light absorbing layer by adopting a hole conductive polymer having a hole conduction characteristic while having a characteristic of additionally absorbing light in the near infrared region that the hole conductor does not absorb in the light absorbing layer,
  • a new photoelectric device and a method of manufacturing the same which can achieve high efficiency by a method of further increasing the density.
  • the present invention has a feature of providing a method of further increasing the efficiency of the optoelectronic device while maintaining a single-cell structure is simple to manufacture.
  • the present invention provides a new optoelectronic device that forms an electron channel in the hole conductive layer like an organic solar cell, and has a band gap that overlaps the wavelength band absorbed by the hole conductor (hole transfer) and the light absorbing layer.
  • a hole-conducting polymer that competitively absorbs light or absorbs light in a long wavelength band of a near infrared region that the light absorbing layer cannot absorb is used as a hole conductor, and further forms hole-holes in the hole conductive layer.
  • An electron channel generated in one hole conductive layer provides a photoelectric device having a novel structure, in which the light absorption wavelength band is wider, further increasing the photoelectric conversion efficiency.
  • the method of manufacturing the optoelectronic device of the present invention may be applied to any conventional method in the art.
  • the electron transporter may be coated and dried on a substrate by using a printing method to form an electron transport layer.
  • the light absorber is coated or the light absorber precursor is coated and calcined or dried to form a light absorbing layer.
  • the electron channel former and the hole conductive polymer are sequentially coated or mixed. It may be coated to prepare a hole conductive layer.
  • a metal oxide more preferably a conventional porous metal oxide can be used, for example Ti oxide, Zn oxide, In oxide, Sn Oxides, W oxides, Nb oxides, Mo oxides, Mg oxides, Zr oxides, Sr oxides, Yr oxides, La oxides, V oxides, Al oxides, Y oxides, Sc oxides, Sm oxides, Ga oxides, In oxides, and SrTi oxides And combinations of one or more thereof.
  • the thickness of the electron transport layer according to the present invention is preferably 0.05 to 10 ⁇ m, the thickness less than 0.05 ⁇ m can not attach a light absorber formed of a sufficient amount of inorganic semiconductor has a disadvantage that the efficiency of the optoelectronic device is reduced In addition, the thickness of more than 10 ⁇ m has a disadvantage in that the distance to transfer the photoelectrons generated from the light to the external circuit is long, which also lowers the efficiency of the optoelectronic device.
  • the particle size of the electron transporter is preferably 5 to 1000 nm, but the particle size of less than 5 nm has a disadvantage that the pores are too small to attach a sufficient amount of light absorber in the pores, the electron carrier per unit area at a particle diameter of more than 1000 nm It is difficult to attach a large amount of the light absorber due to the reduction in the surface area of the photoelectric device, which reduces the efficiency of the photoelectric device.
  • the electron transporter Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide, SrTi oxide, a composite of the oxide and the oxide and the composite may have one or two or more of the inorganic material formed as a coating layer.
  • the pores of the electron transporter formed of the metal oxide may be coated within a very tight range.
  • the light absorber of the present invention is an inorganic semiconductor material that absorbs sunlight to generate an electron-hole pair, and has a small bandgap and a high light absorption coefficient, thereby efficiently absorbing sunlight, and between the electron transporter and the hole conductor. It is preferred that the semiconductor be an inorganic semiconductor having excellent energy band matching between each component and allowing efficient separation and transfer of excitons generated by light.
  • Examples of light absorbers (sensitizers) that absorb electrons and generate electron-holes according to the present invention include CdS, CdSe, CdTe, PbS, PbSe, PbTe, Bi 2 S 3 , Bi 2 Se 3 , InP, InAs, InGaAs , ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, InSb, Si, Ge, AlAs, AlSb, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , Sb 2 Te 3 , SnS x (1 ⁇ x ⁇ 2 ), NiS, CoS, FeS x (1 ⁇ x ⁇ 2 ), In 2 S 3 , MoS, MoSe, Cu 2 S, HgTe, MgSe and one or more selected materials thereof It is preferably a physical or chemical attachment to the surface of the electron transporter has a structure of nanoparticle
  • the band gap means a difference between a conduction band and a valence band of an inorganic semiconductor material, which is a light absorber, and when the size of the band gap or the particle is small depending on the intrinsic properties of the material,
  • the effect of the quantum-confinement effect means a bandgap changed from the intrinsic properties of the material according to the nanoparticle size.
  • the light absorber is physically or chemically attached to the surface of the electron transport layer photoanode to absorb light so that the electrons are well injected into the electron transport layer (layer).
  • the particles of the inorganic semiconductor are preferably attached to the surface of the electron carrier in the form of separate particles of each individual particle, but even if the inorganic semiconductor particles are partially aggregated, there is no big problem.
  • the electron channel forming material for forming the electron channel in the hole conductive layer may cover part and all of the surface of the electron carrier, and may also cover a part of the light absorbing layer or the surface of the light absorber.
  • the electron channel forming material is an electron-hole pair generated by the absorption of light in the hole-conducting polymer of the present invention, which is a hole conductor, so that electrons can be effectively transferred to an electron carrier (layer), thereby providing an external quantum efficiency (external quantum). It can be called hole-electron separator or electron channel material to improve efficiency.
  • the electron channel former is positioned at a position where the lower unoccupied molecular orbital (LUMO) energy band of the hole conductive polymer is higher than the conduction band of the electron carrier to effectively inject the electrons transferred from the hole conductive polymer into the electron transport layer.
  • LUMO lower unoccupied molecular orbital
  • the electron channel forming material according to the present invention may be any material that transfers the separated electrons well to the electron conductive layer while efficiently separating the holes and the electrons from the hole-electron pair.
  • the hole conductive polymer having the characteristics of the present invention competitively absorbs light in the same region as the wavelength band absorbed by the light absorbing layer and transfers holes generated in the light absorbing layer, or absorbs light having a longer wavelength, thereby generating electron-hole pairs. It can be done. It is preferable that the bandgap is smaller than 3.1 eV in order to absorb light and generate an electron-hole pair, having a HOMO higher than the valence band of the light absorber and the HOOC (Highest occupied molecular orbital) of the organic electron channel.
  • P3HT poly [3-hexylthiophene]
  • PCPDTBT poly (2,6- (4,4-bis- (2-ethylhexyl) -4 H -cyclopenta [2,1- b ; 3,4- b ] dithiophene) -alt-4,7 (2,1,3-benzothiadiazole
  • PCPTBT poly ( N -9 ''-heptadecanyl-2,7-carbazole-alt-5,5- (4 ', 7) '-di-2-thienyl-2', 1 ', 3'-benzothiadiazole)
  • PTAA poly (triarylamine)
  • MDMO-PPV poly [2-methoxy-5- (3', 7'-dimethyloctyloxyl) ] -1,4-phenylene vinylene
  • MEH-PPV poly [2-methoxy-5 (2 ''-ethylhexyloxy
  • the composition ratio of the hole conductive polymer and the electron channel forming material is not particularly limited, but 1 to 500 parts by weight, preferably 50 to 200 parts by weight, of the electron channel forming material is used based on 100 parts by weight of the hole conductive polymer. Good to do.
  • the mixing amount of the electron channel forming agent is small, it is difficult to form an efficient electron channel, and when the mixing amount of the electronic channel forming material is too large, there is a problem in that hole transfer of the hole carrier is difficult.
  • the present invention provides a partial or whole portion of a light absorber formed of an inorganic semiconductor (including quantum dot nanoparticles, a discontinuous layer, a continuous layer) and / or an electron carrier formed of a metal oxide that receives electrons to generate electron-hole pairs.
  • An object of the present invention is to provide an optoelectronic device including an electron channel forming a coating layer.
  • the photoelectric device according to the present invention has an electron channel as described above to help effectively transfer charge carriers generated from the hole conductive polymer to the electron carrier of the metal oxide, thereby improving external quantum efficiency. It can be manufactured with high efficiency optoelectronic device.
  • FIG. 1 is an example illustrating a cross-sectional structure of an optoelectronic device according to the present invention.
  • Example 2 shows a value of measuring external quantum efficiency of the photoelectric device according to Example 1 of the present invention.
  • Example 3 shows a value of measuring external quantum efficiency of the photoelectric device according to Example 2 of the present invention.
  • FIG. 4 shows measured values of the external quantum efficiency of the photoelectric device according to Comparative Example 1.
  • porous electron transporter 2 inorganic semiconductor light absorber
  • FIG. 1 is a cross-sectional structure of an optoelectronic device according to an embodiment of the present invention, which includes a porous electron transporter 1, an inorganic semiconductor light absorber 2, a hole conductive polymer 3, an electron channel 4, and a metal electrode ( A photoelectric device having 5) is shown.
  • ethyl cellulose Dissolved 10% by weight of ethyl cellulose in ethyl alcohol in TiO 2 powder with an average particle size of 60 nm (prepared by hydrothermal treatment of titanium perocomplex solution containing 1% by weight based on TiO 2 at 250 ° C for 12 hours).
  • the ethyl cellulose solution was prepared with addition of 5 ml per 1g and TiO 2, Terre pinol (terpinol) the TiO 2 1 g of TiO 2 powder paste by removing the ethyl alcohol, then a solution of 5 g was added to the reduced pressure distillation party.
  • a glass substrate coated with a fluorine-containing tin oxide (FTO; F-doped SnO 2 , 8 ohms / sq, Pilkington, hereinafter FTO substrate) is cut to a size of 25 x 25 mm, and the end is etched to partially remove the FTO. It was.
  • FTO fluorine-containing tin oxide
  • a 50 nm thick, dense TiO 2 thin film was prepared by spray pyrolysis on the cut and partially etched FTO substrate.
  • the spray pyrolysis was performed using a TAA (Titanium acetylacetonate): EtOH (1: 9v / v%) solution, and sprayed for 3 seconds on a FTO substrate placed on a hotplate maintained at 450 ° C. and repeated for 10 seconds. The thickness was adjusted by the method.
  • an electron channel / hole conductive polymer was spin coated by a composite solution of 10 mg of PCBM (phenyl-C 61 -butyricacidmethylester) and 15 mg of P3HT, a hole conductive polymer, dissolved in 1 mL dichlorobenzene.
  • a hole transporter layer which is a composite layer, was formed.
  • the optoelectronic device was completed by Au deposition on a substrate coated with the electron channel former / hole conductive polymer, which is the hole transport layer, using a metal electrode.
  • the external quantum efficiency of the optoelectronic device according to the embodiment is shown in FIG. 2, and the recombination of the hole-electron pair generated by absorbing light in the hole-conducting polymer through the introduction of the electron channel is minimized, and thus the electron outside of the electron generated by the separation of the hole.
  • the external quantum efficiency is about 65% in the region where the hole-conducting polymer is absorbed because it is well transferred to the metal oxide electron transport layer through the furnace electron channel.
  • Example 1 Except not forming the PCBM channel as an electron channel in Example 1, a photoelectric device was manufactured and evaluated in the same manner as in Example 1.
  • the external quantum efficiency of the optoelectronic device according to Comparative Example 1 is shown in FIG. 4 and the contrast with respect to the external quantum efficiency, as shown in Table 1, is an embodiment having an electron channel in the region where absorption of the hole conductive polymer is present. From 65% of 1 to 52%, it can be seen that the external quantum efficiency is greatly reduced.
  • Example 1 Except for replacing the P3HT hole-conducting polymer instead of the P3HT hole-conducting polymer in Example 1 to prepare a photoelectric device in the same manner as in Example 1 and measured the external quantum efficiency as in Example 1.
  • the external quantum efficiency of the optoelectronic device according to the embodiment is shown in FIG. 3, and the recombination of the hole-electron pair generated by absorbing light in the hole-conducting polymer through the introduction of the electron channel is minimized, resulting in the separation of electrons and holes.
  • the external quantum efficiency is about 20% even in the 800 nm area where the light absorber cannot be absorbed because it is well transmitted to the metal oxide electron transporter through the electron channel, and the hole transporter absorbs long-wavelength sunlight in addition to the hole conduction function. Show your contribution.
  • Example 2 Except not forming the PCBM channel as an electron channel in Example 2, and fabricated a photoelectric device in the same manner as in Example 1 and evaluated the performance.
  • External quantum efficiency of the optoelectronic device according to Comparative Example 2 is shown in Figure 5 and the contrast data for the external quantum efficiency is shown in Table 1, Example 2 having an electron channel in the region of the absorption of the hole conductive polymer It can be seen that the external quantum efficiency of is about 20% to almost 0%, which does not produce additional photoelectrons from long-wavelength sunlight.
  • the increase in the external quantum efficiency of the photoelectric device according to Examples 1 to 2 and Comparative Examples 1 to 2 is shown in Table 1, and summarized on a part of the surface of the metal oxide electron transporter and a part of the surface of the entire or inorganic semiconductor light absorber.

Abstract

The present invention relates to a photoelectric device for a solar cell, having a novel structure and good photoconversion efficiency by including a hole conductive layer having an electron channel forming material/hole conductive polymer, and to a method for manufacturing same. More particularly, the present invention relates to a highly efficient photoelectric device including an electron transport layer, a light-absorbing layer, and a hole conductive layer, and to a method for manufacturing same. In the device, a hole conductive polymer, having the capability of absorbing light in a wavelength range from visible light to near-infrared light and having a hole-conducting capability, may absorb light competitively with the light-absorbing layer or may absorb light having a long wavelength that is not absorbed by the light-absorbing layer so as to produce excitons which are electron-hole combinations. In this case, electrons may be transported through the electron channel.

Description

고효율 무/유기 이종접합 무기반도체 감응형 광전소자 및 그 제조방법High efficiency organic / organic heterojunction inorganic semiconductor sensitive photoelectric device and method of manufacturing the same
본 발명은 고효율 무/유기 이종접합 구조의 무기 반도체 나노입자 감응형 광전소자 및 그 제조 방법을 제공하는 것에 관한 것이다. The present invention relates to providing an inorganic semiconductor nanoparticle-sensitized photoelectric device having a high efficiency organic / organic heterojunction structure and a method of manufacturing the same.
보다 상세하게는 전자전달층/광흡수층/홀전도층으로 구성된 광전소자에서, 가시광선에서 근적외선 영역에 있는 파장대역의 광을 흡수하는 능력과 홀을 전도하는 능력을 가진 홀전도성 고분자가 광흡수층에서 흡수하지 못한 빛을 흡수하여 전자-홀 쌍인 엑시톤을 생성하는 경우, 홀전도층에서도 전자채널을 형성하게 되어 전자와 홀을 용이하게 분리되어 광변환 효율이 더욱 증가되는 신규한 구조의 태양전지용 광전소자 및 그 제조 방법에 관한 것이다.More specifically, in the optoelectronic device consisting of an electron transport layer / light absorbing layer / hole conductive layer, a hole conductive polymer having the ability to absorb light in the wavelength band in the near infrared region in visible light and the ability to conduct holes in the light absorbing layer In the case of generating excitons, which are electron-hole pairs, by absorbing light that has not been absorbed, a new structure of a photovoltaic cell having a novel structure in which an electron channel is formed in the hole conducting layer to easily separate electrons and holes to further increase light conversion efficiency And a method for producing the same.
전자를 전달하는 능력을 가진 다공성 광양극(photoanode)에 빛을 흡수하는 염료를 흡착한 후, 그 상부에 전도성 유리 기판을 위치시키고, 액체 전해질을 채운 간단한 구조의 소위 염료감응 태양전지는 오래전부터 알려져 있다. 이러한 구조의 태양전지는 다공성 광양극 표면에 흡착된 염료 분자가 태양 빛의 흡수에 의해 전자-홀 쌍을 생성하게 되고, 전자는 다공성 광양극으로 사용된 반도체 산화물의 전도대로 주입되어 투명 전극으로 전달되어 전류를 발생 시키게 된다. 이와 동시에 산화된 염료 분자는 전해질의 산화-환원쌍에 의해 다시 환원되고 산화된 산화-환원쌍은 광음극(photocathode)으로 전달되어 다시 재생되는 형태로 태양전지가 작동하게 된다. A so-called dye-sensitized solar cell with a simple structure, which absorbs a dye that absorbs light onto a porous photoanode having the ability to transfer electrons, then places a conductive glass substrate thereon and fills a liquid electrolyte, has long been known. have. In the solar cell of this structure, dye molecules adsorbed on the surface of the porous photoanode generate electron-hole pairs by absorption of solar light, and electrons are injected into the conduction band of the semiconductor oxide used as the porous photoanode and transferred to the transparent electrode. To generate a current. At the same time, the oxidized dye molecules are reduced again by the oxidation-reduction pair of the electrolyte and the oxidized oxidation-reduction pair is transferred to the photocathode, whereby the solar cell operates.
그러나 이러한 형태의 태양전지는 액체 전해질의 사용에 의한 실링(sealing)문제와 인공적으로 합성된 유기 염료가 가지는 효율과 안정성의 문제가 발생한다. 따라서 염료대신에 무기반도체 나노입자를 광흡수체로 사용하여 광흡수층을 제조하는 소위 무기반도체 나노입자 태양전지 혹은 양자점 감응형 태양전지에 대하여 많은 연구가 진행되고 있다. However, this type of solar cell has a problem of sealing (sealing) by the use of a liquid electrolyte and problems of efficiency and stability of the artificially synthesized organic dye. Therefore, much research is being conducted on so-called inorganic semiconductor nanoparticle solar cells or quantum dot-sensitized solar cells which manufacture light absorption layers using inorganic semiconductor nanoparticles as light absorbers instead of dyes.
무기반도체 나노입자 태양전지는 기존의 염료감응 태양전지에 사용되는 염료에 비하여 광흡수 계수 값이 높고, 나노 입자 크기 제어를 통해 밴드갭 조절이 용이하며, 쌍극자 분극(dipole moment)이 높아 광에 의하여 생성된 엑시톤의 전자-정공으로의 분리가 상대적으로 용이한 특징이 있다. Inorganic semiconductor nanoparticle solar cells have a higher light absorption coefficient than conventional dye-sensitized solar cells, easy to control bandgap through nanoparticle size control, and high dipole moment. The separation of the resulting excitons into electron-holes is relatively easy.
이러한 무기반도체 나노입자로는 PbSe, PbS, PbTe, CdS, CdSe, CdTe, Sb2S3, Sb2Se3, Cu2S, HgTe 등의 칼코게나이드 (chalcogenide)계가 있다. 이러한 칼코게나이드계의 무기반도체 나노입자는 광양극으로 사용하는 전자전달층을 형성하는 다공성의 전자전달체(electron transporter) 표면에 부착되어 외부 광에 의해서 전자-정공(홀) 쌍을 생성하게 된다. 상기 무기반도체 나노입자의 광흡수체에서 생성된 전자가 광양극의 전자전달체에 잘 전달되기 위해서는 무기반도체 나노입자 광흡수체 전도대가 전자전달체의 전도대 보다 높아야 되며, 그 차이가 클수록, 즉 광흡수체의 전도대가 높을수록 광에 의하여 생성된 광전자를 전자전달체에 잘 주입하게 된다. Such inorganic semiconductor nanoparticles include chalcogenides such as PbSe, PbS, PbTe, CdS, CdSe, CdTe, Sb 2 S 3 , Sb 2 Se 3 , Cu 2 S and HgTe. The chalcogenide-based inorganic semiconductor nanoparticles are attached to the porous electron transporter surface forming the electron transport layer used as the photoanode, thereby generating electron-hole (hole) pairs by external light. In order for the electrons generated in the light absorber of the inorganic semiconductor nanoparticles to be well transmitted to the electron transporter of the photoanode, the inorganic semiconductor nanoparticle light absorber conduction band should be higher than the conduction band of the electron transporter. The higher, the better the photoelectrons generated by the light is injected into the electron transporter.
또한 무기반도체 나노입자 광흡수체에서 광의 흡수에 의해 생성된 정공(홀)이 홀전도층에 효과적으로 전달시키기 위해서는 홀전도층을 형성하는 홀전도체의 가전자대가 무기반도체 나노입자 광흡수체의 가전자대보다 높아야 한다. 이에 더하여 홀전도체 그 자체는 무기반도체 나노입자 광흡수체에서 흡수하는 영역의 광을 흡수하지 않을 만큼 밴드갭이 커야한다. 만약 밴드 갭이 작아 광흡수체가 흡수해야할 광을 흡수하면 광흡수체에서 흡수하는 광이 줄어들게 되어 효율 저하를 가져오게 된다.Also, in order for the holes (holes) generated by the absorption of light in the inorganic semiconductor nanoparticle light absorber to be effectively transmitted to the hole conductive layer, the valence band of the hole conductor forming the hole conductive layer must be higher than that of the inorganic semiconductor nanoparticle light absorber. do. In addition, the hole conductor itself should have a large band gap so as not to absorb light in the region absorbed by the inorganic semiconductor nanoparticle light absorber. If the band gap is small and the light absorber absorbs the light to be absorbed, the light absorbed by the light absorber is reduced, resulting in a decrease in efficiency.
본 발명의 목적은 무기반도체 감응형 태양전지에서, 홀전도층의 홀전도체로 사용하는 홀전도성 고분자가 광을 흡수하는 경우에도 홀전도층 내부에서 전자 채널을 형성하도록 하여 전자와 홀을 분리할 수 있도록 함으로써, 광전특성이 우수하게 유지하게 하는 광전소자 제조방법을 제공하는 것이다. An object of the present invention is to separate electrons and holes by forming an electron channel inside the hole conductive layer even when the hole conductive polymer used as the hole conductor of the hole conductive layer absorbs light in the inorganic semiconductor sensitive solar cell. The present invention provides a method of manufacturing an optoelectronic device that maintains excellent photoelectric characteristics.
또한 본 발명은 반도체 나노입자 광흡수층에서 흡수하지 못한 근적외선 영역의 장파장 빛을 추가적으로 홀전도층에서 흡수하는 경우에도 홀전도층 내부에서 전자 채널을 형성하도록 하여 전자와 홀을 분리할 수 있도록 함으로써, 광전특성이 우수하게 유지하게 하는 광전소자 제조방법을 제공하는 것이다. In addition, the present invention allows electrons and holes to be separated by forming electron channels inside the hole conductive layer even when the long wavelength light in the near infrared region, which is not absorbed by the semiconductor nanoparticle light absorbing layer, is additionally absorbed by the hole conductive layer. It is to provide a method for manufacturing an optoelectronic device that maintains excellent characteristics.
상기의 과제를 달성하기 위하여 많은 연구를 한 결과, 본 발명에 따른 광전소자는, 전자전달층, 전자전달층을 구성하는 전자전달체(electron transporter)의 표면에 부착되는 무기반도체 나노입자의 광흡수층 및 홀전도층을 포함하여 이루어지고, 상기 홀전도층은 광흡수층에서 생성된 정공(홀)을 전달하는 홀전도체와 홀전도층의 내부에 전자채널을 형성하여 전자를 전달하는 전자채널형성재를 포함하는 것이다.As a result of much research in order to achieve the above object, the photoelectric device according to the present invention, an electron transport layer, a light absorbing layer of inorganic semiconductor nanoparticles attached to the surface of the electron transporter (electron transporter) constituting the electron transport layer and Comprising a hole conductive layer, the hole conductive layer includes a hole conductor for transmitting holes (holes) generated in the light absorption layer and an electron channel forming material for transmitting electrons by forming an electron channel in the hole conductive layer. It is.
본 발명에서는 상기 전자전달층을 이루은 전자전달체는 밴드갭이 크고 전자를 전달하면서 광흡수용 나노 무기반도체 입자(광흡수체, sensitizer)를 표면에 다량 부착이 가능한 다공성 금속 산화물(광양극 전자 전달체)이며, 상기 광흡수층은 상기 전자전달체의 표면에 흡착되어 있는 광흡수체로 된 층을 의미한다. In the present invention, the electron transporter constituting the electron transport layer is a porous metal oxide (photoanode electron transporter) capable of attaching a large amount of light-absorbing nano-inorganic semiconductor particles (light absorber, sensitizer) to the surface while transferring electrons. The light absorbing layer refers to a layer made of a light absorbing body adsorbed on the surface of the electron transporting body.
본 발명에 따른 광전소자는, 밴드갭이 크고 전자를 전달하면서 광흡수용 나노 무기반도체 입자를 표면에 다량 부착이 가능한 다공성 금속 산화물(광양극 전자 전달체)의 전자전달층과 넓은 파장대역의 빛을 받아 전자와 정공(홀)을 형성하는 무기 반도체 나노입자로 된 광흡수체로 되는 광흡수층 및 홀전도층을 포함하며, 상기 홀전도층은 광흡수층에서 생성된 홀을 전달하는 홀전도성고분자와 홀전도층 내부에 전자 채널을 형성하여 홀전도층에서 광을 흡수하여 생성된 전자를 전달하는 기능을 하는 전자채널형성재를 포함하고 있다. The optoelectronic device according to the present invention has a large bandgap and transmits electrons and a light having a broad wavelength band of an electron transport layer of a porous metal oxide (photocathode electron transporter) capable of attaching a large amount of light-absorbing nano inorganic semiconductor particles to a surface thereof. A light absorbing layer and a hole conducting layer, which are light absorbers made of inorganic semiconductor nanoparticles that receive electrons and form holes (holes), wherein the hole conducting layer transfers holes generated in the light absorbing layer, and hole conduction. An electron channel forming material is formed to form an electron channel inside the layer to absorb the light in the hole conducting layer and transfer the generated electrons.
일반적으로 홀전도성 고분자는 광흡수체가 흡수하는 파장대역의 빛을 흡수하지 않도록 밴드갭이 매우 큰 물질을 사용하므로, 그러한 특성을 가지는 홀전도체가 매우 제한적이어서 그 선택에 한계를 가지므로 우수한 특성의 광전소자를 구성하는 물질의 사용에 제한을 받는 문제점이 있다. 그러나 본 발명에서는 상기의 전자채널형성재를 홀전도제인 홀전도성 고분자와 혼합 또는 함입시킴으로서, 홀전도체로 사용한 홀전도성 고분자가 광흡수층에서 흡수하는 영역의 빛을 경쟁적으로 흡수하는 경우에도, 광전소자의 효율저하를 초래하는 소위 필터 효과를 제거하거나 최소화하여, 광효율을 증가시키는 새로운 광전소자 및 이를 제조하는 방법을 제공할 수 있게 된다. 또한 본 발명은 홀전도체가 광흡수층에서 흡수하지 못하는 근적외선 영역의 빛을 추가적으로 흡수하는 특성을 가지면서 홀전도 특성을 가지는 홀전도성 고분자를 채택하는 것에 의해서도 광흡수층에서 전자와 홀을 분리하도록 함으로서, 광전류 밀도를 더욱 증가시키는 방법으로 고효율화를 얻을 수 있는 새로운 광전소자 및 그의 제조방법을 제공한다. In general, since the hole conductive polymer uses a material having a very large band gap so as not to absorb light in the wavelength band absorbed by the light absorber, the hole conductor having such characteristics is very limited and thus the selection thereof is limited. There is a problem that the use of the material constituting the device is limited. However, in the present invention, by mixing or incorporating the electron channel forming material with a hole conductive polymer, which is a hole conductive agent, even when the hole conductive polymer used as the hole conductor absorbs light in a region absorbed by the light absorption layer, It is possible to provide a new optoelectronic device and a method of manufacturing the same, which eliminates or minimizes the so-called filter effect that causes efficiency deterioration. In addition, the present invention is to separate the electrons and holes in the light absorbing layer by adopting a hole conductive polymer having a hole conduction characteristic while having a characteristic of additionally absorbing light in the near infrared region that the hole conductor does not absorb in the light absorbing layer, Provided are a new photoelectric device and a method of manufacturing the same, which can achieve high efficiency by a method of further increasing the density.
따라서 본 발명은 제조가 간단한 단일셀 구조를 유지하면서 광전소자를 더욱 고효율화하는 방법을 제공하는 특징을 가진다. Therefore, the present invention has a feature of providing a method of further increasing the efficiency of the optoelectronic device while maintaining a single-cell structure is simple to manufacture.
결국 본 발명은 홀전도층에서도 유기태양전지와 같이 전자 채널을 형성하도록 하는 새로운 광전소자를 제공하는 것으로서, 홀전도체(hole transfer)로 광흡수층이 흡수하는 파장대역과 겹치는 밴드갭을 가져 광흡수층과 경쟁적으로 광을 흡수하거나 또는 광흡수층이 흡수하지 못한 근적외선 영역의 장파장대역의 광을 흡수하는 홀전도성 고분자를 홀전도체로 사용하고 이를 홀전도층에서 홀-정공을 추가적으로 형성하게 하여 본 발명에서 형성하도록 한 홀전도층 내에 생성된 전자채널에 의해, 광흡수 파장 대역이 넓게 하여 광전 변환 효율을 더욱 더 높게 하는, 신규한 구조의 광전소자를 제공한다.After all, the present invention provides a new optoelectronic device that forms an electron channel in the hole conductive layer like an organic solar cell, and has a band gap that overlaps the wavelength band absorbed by the hole conductor (hole transfer) and the light absorbing layer. In the present invention, a hole-conducting polymer that competitively absorbs light or absorbs light in a long wavelength band of a near infrared region that the light absorbing layer cannot absorb is used as a hole conductor, and further forms hole-holes in the hole conductive layer. An electron channel generated in one hole conductive layer provides a photoelectric device having a novel structure, in which the light absorption wavelength band is wider, further increasing the photoelectric conversion efficiency.
이하, 본 발명의 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략하여 설명한다.Hereinafter, unless there is another definition in the technical terms and scientific terms of the present invention, it has the meaning commonly understood by those skilled in the art to which the present invention belongs, and the gist of the present invention in the following description and the accompanying drawings. Description of well-known functions and configurations that may unnecessarily obscure the description will be omitted.
본 발명의 상기 광전소자의 제조방법은 이 기술 분야의 통상의 방법이라면 어느 것이라도 적용가능하며, 예를 들면, 기판상에 전자전달체를 프린팅기법을 이용하여 코팅 및 건조하여 전자전달층을 형성하고, 상기 전자전달체가 코팅된 기판상에, 광흡수체를 코팅하거나 광흡수체 전구체를 코팅하고 소성 또는 건조하여 광흡수층을 형성하는 단계를 거치고, 이어서, 전자채널형성재 및 홀전도성 고분자를 차례로 코팅하거나 혼합 코팅하여 홀전도층을 제조할 수 있다. The method of manufacturing the optoelectronic device of the present invention may be applied to any conventional method in the art. For example, the electron transporter may be coated and dried on a substrate by using a printing method to form an electron transport layer. On the substrate coated with the electron transporter, the light absorber is coated or the light absorber precursor is coated and calcined or dried to form a light absorbing layer. Then, the electron channel former and the hole conductive polymer are sequentially coated or mixed. It may be coated to prepare a hole conductive layer.
상세하게, 본 발명에 따른 전자전달층(electron transporting layer)의 전자전달체로는 통상 금속산화물, 더욱 좋게는 통상의 다공성금속산화물을 사용할 수 있으며, 예를 들면 Ti산화물, Zn산화물, In산화물, Sn산화물, W산화물, Nb산화물, Mo산화물, Mg산화물, Zr산화물, Sr산화물, Yr산화물, La산화물, V산화물, Al산화물, Y산화물, Sc산화물, Sm산화물, Ga산화물, In산화물, 및 SrTi산화물 및 이들의 복합물 중에서 하나 이상 선택된 것이 사용 가능하다. Specifically, as the electron transporter of the electron transporting layer (electron transporting layer) according to the present invention, a metal oxide, more preferably a conventional porous metal oxide can be used, for example Ti oxide, Zn oxide, In oxide, Sn Oxides, W oxides, Nb oxides, Mo oxides, Mg oxides, Zr oxides, Sr oxides, Yr oxides, La oxides, V oxides, Al oxides, Y oxides, Sc oxides, Sm oxides, Ga oxides, In oxides, and SrTi oxides And combinations of one or more thereof.
또한 본 발명에 따른 전자전달층의 두께는 0.05 내지 10 ㎛인 것이 바람직하며, 0.05 ㎛ 미만의 두께에서는 충분한 양의 무기 반도체로 형성되는 광 흡수체를 부착할 수 없어 광전소자의 효율이 저하되는 단점이 있고 10 ㎛를 초과하는 두께에서는 광으로부터 발생된 광전자를 외부 회로까지 전달시키는 거리가 길어지게 되어 역시 광전소자의 효율이 저하되는 단점이 있다.In addition, the thickness of the electron transport layer according to the present invention is preferably 0.05 to 10 ㎛, the thickness less than 0.05 ㎛ can not attach a light absorber formed of a sufficient amount of inorganic semiconductor has a disadvantage that the efficiency of the optoelectronic device is reduced In addition, the thickness of more than 10 ㎛ has a disadvantage in that the distance to transfer the photoelectrons generated from the light to the external circuit is long, which also lowers the efficiency of the optoelectronic device.
또한 상기 전자전달체의 입경은 5 내지 1000 nm 인 것이 좋은데, 5 nm 미만의 입경에서는 공극이 너무 작아서 공극 속에 충분한 양의 광 흡수체가 부착될 수 없는 단점이 있고 1000 nm 초과의 입경에서는 단위 면적당 전자전달체의 표면적이 줄어들어 광 흡수체를 많은 양 부착하기 어려워 광전소자의 효율이 감소하는 단점이 있다.In addition, the particle size of the electron transporter is preferably 5 to 1000 nm, but the particle size of less than 5 nm has a disadvantage that the pores are too small to attach a sufficient amount of light absorber in the pores, the electron carrier per unit area at a particle diameter of more than 1000 nm It is difficult to attach a large amount of the light absorber due to the reduction in the surface area of the photoelectric device, which reduces the efficiency of the photoelectric device.
또한 상기 전자전달체는 입자간 계면 접촉을 향상시키기 위하여, Ti산화물, Zn산화물, In산화물, Sn산화물, W산화물, Nb산화물, Mo산화물, Mg산화물, Zr산화물, Sr산화물, Yr산화물, La산화물, V산화물, Al산화물, Y산화물, Sc산화물, Sm산화물, Ga산화물, In산화물, SrTi산화물, 상기 산화물의 복합물 및 상기 산화물과 복합물이 코팅층으로 형성된 무기물 중에서 하나 또는 2 이상의 것을 가질 수 있다. 통상적으로 계면 접촉의 향상을 위해서는 상기 금속 산화물로 형성되는 전자전달체의 공극을 꽉 매우지 않는 범위 내에서 코팅 할 수 있다. In addition, the electron transporter, Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide, SrTi oxide, a composite of the oxide and the oxide and the composite may have one or two or more of the inorganic material formed as a coating layer. In general, in order to improve interfacial contact, the pores of the electron transporter formed of the metal oxide may be coated within a very tight range.
본 발명의 상기 광흡수체는 태양광을 흡수하여 전자-홀 쌍을 생성하는 무기 반도체 물질로서, 밴드갭 (bandgap)이 작고 광흡수 계수가 높아 태양광을 효율적으로 흡수하면서, 전자전달체와 홀전도체 사이에 위치하여 각 요소 성분 간 에너지 밴드 매칭이 우수하여, 광에 의하여 생성된 엑시톤의 효율적인 분리 및 전달이 가능한 무기 반도체인 것이 바람직하다.The light absorber of the present invention is an inorganic semiconductor material that absorbs sunlight to generate an electron-hole pair, and has a small bandgap and a high light absorption coefficient, thereby efficiently absorbing sunlight, and between the electron transporter and the hole conductor. It is preferred that the semiconductor be an inorganic semiconductor having excellent energy band matching between each component and allowing efficient separation and transfer of excitons generated by light.
본 발명에 따른 태양광을 흡수하여 전자-홀을 생성하는 광흡수체(sensitizer)의 예로는 CdS, CdSe, CdTe, PbS, PbSe, PbTe, Bi2S3, Bi2Se3, InP, InAs, InGaAs, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, InSb, Si, Ge, AlAs, AlSb, InCuS2, In(CuGa)Se2, Sb2S3, Sb2Se3, Sb2Te3, SnSx(1≤x≤2), NiS, CoS, FeSx(1≤x≤2), In2S3, MoS, MoSe, Cu2S, HgTe, MgSe 및 이들의 합금에서 하나 또는 둘 이상 선택된 물질인 것이 바람직하며 전자전달체 표면에 물리적 혹은 화학적으로 부착되어 나노입자, 불연속층 또는 연속층의 구조를 가진다.Examples of light absorbers (sensitizers) that absorb electrons and generate electron-holes according to the present invention include CdS, CdSe, CdTe, PbS, PbSe, PbTe, Bi 2 S 3 , Bi 2 Se 3 , InP, InAs, InGaAs , ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, InSb, Si, Ge, AlAs, AlSb, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , Sb 2 Te 3 , SnS x (1 ≦ x ≦ 2 ), NiS, CoS, FeS x (1 ≦ x ≦ 2 ), In 2 S 3 , MoS, MoSe, Cu 2 S, HgTe, MgSe and one or more selected materials thereof It is preferably a physical or chemical attachment to the surface of the electron transporter has a structure of nanoparticles, discontinuous layer or continuous layer.
상기 밴드갭은 광흡수체인 무기 반도체 물질이 가지는 전도대 띠(conduction band)와 가전자대 띠 (valence band)의 차이를 의미하며, 물질 고유의 특성에 의존한 밴드갭 또는 입자의 크기가 작은 경우 양자구속효과(Quantum-confinement effect)에 의해 나노입자 크기에 따라 물질 고유의 특성으로부터 변화된 밴드갭을 의미한다. The band gap means a difference between a conduction band and a valence band of an inorganic semiconductor material, which is a light absorber, and when the size of the band gap or the particle is small depending on the intrinsic properties of the material, By the effect of the quantum-confinement effect means a bandgap changed from the intrinsic properties of the material according to the nanoparticle size.
상기 광흡수체는 전자전달층 광양극 표면에 물리적 혹은 화학적으로 부착되어 광을 흡수하여 생성된 전자가 전자전달체(층)로 잘 주입 되도록 한다. 이때 무기 반도체의 입자는 각각의 입자가 각각 독립된 개별 입자의 분리된 형태로 전자전달체 표면에 부착되는 것이 바람직하지만, 무기반도체 입자가 일부 응집되는 경우에도 전자 전달체에 부착되어 있으면 큰 문제가 없다. The light absorber is physically or chemically attached to the surface of the electron transport layer photoanode to absorb light so that the electrons are well injected into the electron transport layer (layer). In this case, the particles of the inorganic semiconductor are preferably attached to the surface of the electron carrier in the form of separate particles of each individual particle, but even if the inorganic semiconductor particles are partially aggregated, there is no big problem.
본 발명의 구성에서 홀전도층에서 전자채널을 형성하는 전자채널형성재는 전자전달체 표면의 일부 및 전부를 덮을 수 있으며, 광흡수층이나 광흡수체의 표면의 일부를 덮을 수도 있다. 상기 전자채널형성재는 홀전도체인 본 발명의 홀전도성 고분자에서 광의 흡수에 의해 생성된 전자-정공 쌍에서 전자를 전달받아 전자전달체(층)에 효과적으로 전달될 수 있도록 해 주어, 외부 양자 효율 (external quantum efficiency)을 향상 시킬 수 있는 것으로 홀-전자 분리제 혹은 전자채널재라고 할 수 있다. In the configuration of the present invention, the electron channel forming material for forming the electron channel in the hole conductive layer may cover part and all of the surface of the electron carrier, and may also cover a part of the light absorbing layer or the surface of the light absorber. The electron channel forming material is an electron-hole pair generated by the absorption of light in the hole-conducting polymer of the present invention, which is a hole conductor, so that electrons can be effectively transferred to an electron carrier (layer), thereby providing an external quantum efficiency (external quantum). It can be called hole-electron separator or electron channel material to improve efficiency.
본 발명에서 전자채널형성재는 홀전도성 고분자에서 전달받은 전자를 전자전달층에 효과적으로 주입하기 위해 홀전도성 고분자의 LUMO (Lowest Unoccupied Molecular Orbital) 에너지 밴드가 전자 전달체의 전도대 (Conduction energy band)보다 높은 곳에 위치하는 물질이 바람직하다.In the present invention, the electron channel former is positioned at a position where the lower unoccupied molecular orbital (LUMO) energy band of the hole conductive polymer is higher than the conduction band of the electron carrier to effectively inject the electrons transferred from the hole conductive polymer into the electron transport layer. Preferred substances are.
본 발명에 따른 전자채널형성재는 홀-전자쌍에서 홀과 전자로 효율 좋게 분리하면서 분리된 전자를 전자전도층으로 잘 전달하는 물질이면 모두 가능하다. 일예로, C60 풀러렌, C70 풀러렌을 포함한 이들의 유도체 등을 예로 들 수 있고, 또한 n-형 유기반도체 물질인 이들의 예를 들면 Pc2Lu(bisphthalocyanine complexes of lutetium), Pc2Tm(bisphthalocyanine complexes of thulium), TCNQ(Tetracyanoquinodimethane),PTCDI-Ph(2,9-Diphenylanthra (2,1,9-def:6,5,10-d'e'f')diisoquinoline-1,3,8,10(2H,9H)-tetrone), TCNNQ(11,11,12,12-tetracyano-1,4-naphthaquinodimethane), NTCDI(Naphthalene 1,4,5,8-tetracarboxylic diimide), PTCDA(perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride), F16CuPc(copper hexadecafluorophthalocyanine),NYCDI-C8F,DHF-6T, Pentacene, PTCDI-C8, quinodimethane, BBL, DFH-4T, DFH-5T, DFH-6T 및 PCBM 등을 예로 들 수 있다.The electron channel forming material according to the present invention may be any material that transfers the separated electrons well to the electron conductive layer while efficiently separating the holes and the electrons from the hole-electron pair. For example, C60 fullerene, derivatives thereof including C70 fullerene, and the like, and examples thereof, which are n-type organic semiconductor materials, for example, Pc2Lu (bisphthalocyanine complexes of lutetium), Pc2Tm (bisphthalocyanine complexes of thulium), and TCNQ Tetracyanoquinodimethane, PTCDI-Ph (2,9-Diphenylanthra (2,1,9-def: 6,5,10-d'e'f ') diisoquinoline-1,3,8,10 (2H, 9H)- tetrone), TCNNQ (11,11,12,12-tetracyano-1,4-naphthaquinodimethane), NTCDI (Naphthalene 1,4,5,8-tetracarboxylic diimide), PTCDA (perylene-3,4,9,10-tetracarboxylic -3,4,9,10-dianhydride), F16CuPc (copper hexadecafluorophthalocyanine), NYCDI-C8F, DHF-6T, Pentacene, PTCDI-C8, quinodimethane, BBL, DFH-4T, DFH-5T, DFH-6T and PCBM etc. For example.
본 발명의 특성을 가지는 홀전도성 고분자는 광흡수체에서 생성된 홀의 전달 및 광흡수층에서 흡수하는 파장대역과 동일한 영역의 광을 경쟁적으로 흡수하거나 그 보다 더 장파장의 광을 흡수하여 전자-정공 쌍을 생성해 줄 수 있는 물질이다. 광 흡수체의 가전도대 (valence band) 및 유기계 전자채널의 HOMO (Highest occupied molecular orbital)보다 높은 HOMO를 가지며 광을 흡수하여 전자-정공쌍을 생성하기 위하여 밴드갭이 3.1eV 보다 작은 것이 바람직하다. 예를 들면, P3HT (poly[3-hexylthiophene]), PCPDTBT (poly(2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b ]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)), PCPTBT (poly (N-9''-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)), PTAA (poly(triarylamine)),MDMO-PPV(poly[2-methoxy-5-(3’,7’- dimethyloctyloxyl)]-1,4-phenylene vinylene), MEH-PPV (poly[2-methoxy -5-(2’'-ethylhexyloxy)-p-phenylene vinylene]), P3OT(poly(3-octyl thiophene)), PPV (poly(p-phenylene vinylene)),TFB (poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl)diphenyl amine),POT( poly(octyl thiophene)), PCPDTBT(Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2,6-diyl]]), PCDTBT(Poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]) 및 이들의 복합물에서 선택되는 하나 이상의 물질이 바람직 하다. 기타 홀전도성 고분자의 예로는 PTPTB, PSBTBT, P2, PBBTDPP2, PDPP-BPD2, PFPDT, PFDTBT, PSiF-DBT, APFO-15, HXS-1, PFO-PTBT, APFO-Green2, PBEHTB, PF-co-DTB, PFO-SeBT등을 예로들 수 있지만 이에 한정되는 것은 아니다.The hole conductive polymer having the characteristics of the present invention competitively absorbs light in the same region as the wavelength band absorbed by the light absorbing layer and transfers holes generated in the light absorbing layer, or absorbs light having a longer wavelength, thereby generating electron-hole pairs. It can be done. It is preferable that the bandgap is smaller than 3.1 eV in order to absorb light and generate an electron-hole pair, having a HOMO higher than the valence band of the light absorber and the HOOC (Highest occupied molecular orbital) of the organic electron channel. For example, P3HT (poly [3-hexylthiophene]), PCPDTBT (poly (2,6- (4,4-bis- (2-ethylhexyl) -4 H -cyclopenta [2,1- b ; 3,4- b ] dithiophene) -alt-4,7 (2,1,3-benzothiadiazole), PCPTBT (poly ( N -9 ''-heptadecanyl-2,7-carbazole-alt-5,5- (4 ', 7) '-di-2-thienyl-2', 1 ', 3'-benzothiadiazole)), PTAA (poly (triarylamine)), MDMO-PPV (poly [2-methoxy-5- (3', 7'-dimethyloctyloxyl) ] -1,4-phenylene vinylene), MEH-PPV (poly [2-methoxy-5 (2 ''-ethylhexyloxy) -p- phenylene vinylene]), P3OT (poly (3-octyl thiophene)), PPV ( poly ( p -phenylene vinylene)), TFB (poly (9,9'-dioctylfluorene-co-N- (4-butylphenyl) diphenyl amine), POT (poly (octyl thiophene)), PCPDTBT (Poly [2,1, 3-benzothiadiazole-4,7-diyl [4,4-bis (2-ethylhexyl) -4H-cyclopenta [2,1-b: 3,4-b '] dithiophene-2,6-diyl]]), PCDTBT (Poly [[9- (1-octylnonyl) -9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]) And one or more materials selected from these composites.Other examples of hole conducting polymers include PTPTB, PSBTBT, P2, PBBTDPP2, PDPP-BPD2, PFPDT, PFDTBT, PSiF-DBT, APFO-15, HXS-1, PFO-PTBT, APFO-Green2, PBEHTB, PF-co-DTB, PFO-SeBT, etc. It is not limited.
본 발명에 있어서, 상기 홀전도성 고분자와 전자채널형성재의 사용조성비는 크게 제한되지 않지만, 홀전도성 고분자 100중량부에 대하여 전자채널형성재를 1 내지 500중량부, 바람직하게는 50 내지 200중량부 사용하는 것이 좋다. 전자채널형성제의 혼합양이 적으면 효율적인 전자채널의 형성이 어려우며, 전자재널형성재의 혼합 양이 너무 많으면 정공전달체의 정공전달을 어렵게 하는 문제가 있다.In the present invention, the composition ratio of the hole conductive polymer and the electron channel forming material is not particularly limited, but 1 to 500 parts by weight, preferably 50 to 200 parts by weight, of the electron channel forming material is used based on 100 parts by weight of the hole conductive polymer. Good to do. When the mixing amount of the electron channel forming agent is small, it is difficult to form an efficient electron channel, and when the mixing amount of the electronic channel forming material is too large, there is a problem in that hole transfer of the hole carrier is difficult.
본 발명은 태양광을 입력받아 전자-홀 쌍을 생성하는 무기 반도체(양자점 나노입자, 불연속층, 연속층 포함)로 형성되는 광 흡수제의 부분 및/또는 금속 산화물로 형성된 전자 전달체에 부분 또는 전체로 코팅층을 형성하는 전자채널을 포함하여 형성되는 광전 소자를 제공하는 것에 특징이 있다. The present invention provides a partial or whole portion of a light absorber formed of an inorganic semiconductor (including quantum dot nanoparticles, a discontinuous layer, a continuous layer) and / or an electron carrier formed of a metal oxide that receives electrons to generate electron-hole pairs. An object of the present invention is to provide an optoelectronic device including an electron channel forming a coating layer.
본 발명에 따른 광전소자는 상기와 같이 홀전도층도 전자채널을 가짐으로써 홀전도 고분자에서 생성된 전하운반자(charge carrier)를 금속 산화물의 전자 전달체에 효과적으로 전달 되도록 도와주어, 외부 양자 효율을 개선할 수 있어 고효율 광전소자를 제조 할 수 있는 특징이 있다.The photoelectric device according to the present invention has an electron channel as described above to help effectively transfer charge carriers generated from the hole conductive polymer to the electron carrier of the metal oxide, thereby improving external quantum efficiency. It can be manufactured with high efficiency optoelectronic device.
도 1은 본 발명에 따른 광전소자의 단면 구조를 도시한 일 예이다.1 is an example illustrating a cross-sectional structure of an optoelectronic device according to the present invention.
도 2는 본 발명의 실시예 1에 따른 광전소자의 외부양자효율을 측정한 값을 나타낸다.2 shows a value of measuring external quantum efficiency of the photoelectric device according to Example 1 of the present invention.
도 3은 본 발명의 실시예 2에 따른 광전소자의 외부양자효율을 측정한 값을 나타낸다.3 shows a value of measuring external quantum efficiency of the photoelectric device according to Example 2 of the present invention.
도 4는 비교예 1에 따른 광전소자의 외부양자효율을 측정한 값을 나타낸다.4 shows measured values of the external quantum efficiency of the photoelectric device according to Comparative Example 1. FIG.
도 5는 비교예 1에 따른 광전소자의 외부양자효율을 측정한 값을 나타낸다.5 shows a value of measuring external quantum efficiency of the photoelectric device according to Comparative Example 1.
(부호의 설명)(Explanation of the sign)
1 : 다공성 전자 전달체 2 : 무기반도체 광흡수체1: porous electron transporter 2: inorganic semiconductor light absorber
3 : 전자 채널 4 : 홀전도성 고분자3: electron channel 4: hole conductive polymer
5 : 금속 전극5: metal electrode
본 발명은 이하 첨부한 도면들을 참조하여 본 발명의 태양전지 및 그 제조방법을 상세히 설명한다. 다음에 소개되는 도면들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다. 따라서, 본 발명은 이하 제시되는 도면들에 한정되지 않고 다른 형태로 구체화될 수도 있으며, 이하 제시되는 도면들은 본 발명의 사상을 명확히 하기 위해 과장되어 도시될 수 있다. The present invention will now be described in detail with reference to the accompanying drawings, the solar cell of the present invention and a method of manufacturing the same. The drawings introduced below are provided by way of example so that the spirit of the invention to those skilled in the art can fully convey. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention.
도 1 을 기반으로 상술한 본 발명의 핵심 사상에 따른 일 제조 예에 의거하여 더욱 구체화하여 상술한다. Based on the manufacturing example according to the core idea of the present invention described above based on Figure 1 will be described in more detail.
도 1은 본 발명에 따른 광전소자의 단면 구조를 도시한 일 예로서, 다공성 전자 전달체 (1), 무기 반도체 광흡수체(2), 홀전도성 고분자 (3), 전자채널(4) 및 금속전극 (5)를 가지는 광전소자를 나타내고 있다. 1 is a cross-sectional structure of an optoelectronic device according to an embodiment of the present invention, which includes a porous electron transporter 1, an inorganic semiconductor light absorber 2, a hole conductive polymer 3, an electron channel 4, and a metal electrode ( A photoelectric device having 5) is shown.
이하에서는 본 발명에 따른 광전자소자의 제조방법에 대하여 설명하며, 본 제조예 및 실시예는 그것에 한정하는 것이 아니며, 통상의 지식을 가진 자라면 그로부터 다양하게 변경하여 실시할 수 있다.Hereinafter, a method of manufacturing an optoelectronic device according to the present invention will be described. The present manufacturing examples and examples are not limited thereto, and those skilled in the art may variously change the present invention.
[제조예] 금속 산화물 전자전달체 페이스트 제조Preparation Example Metal Oxide Electron Carrier Paste Preparation
평균 입자크기 60 nm의 TiO2 분말(TiO2 기준으로 1 중량%가 용해된 titanium perocomplex 수용액을 250 ℃에서 12 시간 수열처리하여 제조)에 에틸 셀룰로오스(ethyl cellulose)가 10 중량 %로 에틸알콜에 용해된 에틸 셀룰로오스 용액을 TiO2 1g당 5 ml 첨가하고, 테르피놀(terpinol)을 TiO2 1 g당 5 g 첨가하여 혼합한 후, 에틸 알콜을 감압 증류법으로 제거하여 TiO2 분말 페이스트를 제조하였다.Dissolved 10% by weight of ethyl cellulose in ethyl alcohol in TiO 2 powder with an average particle size of 60 nm (prepared by hydrothermal treatment of titanium perocomplex solution containing 1% by weight based on TiO 2 at 250 ° C for 12 hours). the ethyl cellulose solution was prepared with addition of 5 ml per 1g and TiO 2, Terre pinol (terpinol) the TiO 2 1 g of TiO 2 powder paste by removing the ethyl alcohol, then a solution of 5 g was added to the reduced pressure distillation party.
[실시예 1] 광전 소자 제작Example 1 Optoelectronic Device Fabrication
1) 에칭 공정1) etching process
불소 함유 산화주석이 코팅된 유리 기판(FTO; F-doped SnO2, 8 ohms/sq, Pilkington, 이하 FTO 기판)을 25 x 25 mm 크기로 절단한 후, 끝 부분을 에칭하여 부분적으로 FTO를 제거 하였다. A glass substrate coated with a fluorine-containing tin oxide (FTO; F-doped SnO 2 , 8 ohms / sq, Pilkington, hereinafter FTO substrate) is cut to a size of 25 x 25 mm, and the end is etched to partially remove the FTO. It was.
2) 재결합 방지막 증착 공정2) Recombination prevention film deposition process
절단 및 부분 에칭된 FTO 기판 위에 재결합 방지막으로서 50 nm 두께의 치밀한 구조의 TiO2 박막을 분무 열분해법으로 제조하였다. 상기 분무 열분해는 TAA(Titanium acetylacetonate):EtOH(1:9v/v%) 용액을 이용하여 수행되었으며, 450 ℃로 유지된 열판위에 올려진 FTO 기판위에 3 초간 분무하고 10초간 정지하는 방법을 되풀이하는 방법으로 두께를 조절하였다.A 50 nm thick, dense TiO 2 thin film was prepared by spray pyrolysis on the cut and partially etched FTO substrate. The spray pyrolysis was performed using a TAA (Titanium acetylacetonate): EtOH (1: 9v / v%) solution, and sprayed for 3 seconds on a FTO substrate placed on a hotplate maintained at 450 ° C. and repeated for 10 seconds. The thickness was adjusted by the method.
3) 금속 산화물 전자전달체 프린팅 공정3) Metal Oxide Electron Transfer Printing Process
기판의 TiO2 박막 위에, 제조예에서 제조된 TiO2 분말 페이스트를 이용하여 스크린 프린팅법으로 코팅하고 500 ℃에서 30 분 동안 열처리한 후, 20 mM TiCl4 수용액에 열처리된 기판을 담근 후 약 12 시간 동안 방치한 후, 탈이온수와 에탄올로 세척 및 건조하고 다시 500 ℃에서 30분 동안 열처리하여, 비표면적이 50 m2/g이며, 두께가 1 um인 다공성 전자전달체가 코팅된 기판을 제조하였다.On the TiO 2 thin film of the substrate, coated with the screen printing method using the TiO 2 powder paste prepared in Preparation Example, heat-treated at 500 ℃ for 30 minutes, and then immersed the heat-treated substrate in 20 mM TiCl 4 aqueous solution about 12 hours After being left for a while, washed and dried with deionized water and ethanol and heat-treated again at 500 ° C. for 30 minutes to prepare a substrate coated with a porous electron transporter having a specific surface area of 50 m 2 / g and a thickness of 1 um.
4) 광흡수체의 제조4) Preparation of Light Absorber
2.5 mL의 아세톤에 SbCl3(Junsei) 0.65 g을 첨가하여 용해한 제1전구체 용액과 25 mL의 이온교환수에 Na2S2O3(Aldrich) 3.95 g을 녹인 제2 전구체 용액을 혼합하여 광흡수체용 혼합용액을 제조하고, 다공성 전자 전달체가 코팅된 상기 기판을 제조된 상기 광흡수체 혼합용액에 함침시키고, 10 ℃ 이하의 온도에서 3시간 방치하는 화학적 용액성장법(CBD)으로 Sb2S3 광흡수체를 형성하였다. 형성된 Sb2S3 광흡수체는 Ar 분위기에서 330℃에서 30분 동안 어닐링(annealing)하여 제조하였다. SbCl in 2.5 mL acetone3(Junsei) To the first precursor solution dissolved by adding 0.65 g of Na and 25 mL of ion-exchanged water,2S2O3(Aldrich) 3.95 g of the second precursor solution was dissolved in the mixture to prepare a light absorber mixed solution, the substrate coated with a porous electron transporter was impregnated into the prepared light absorber mixed solution, and left for 3 hours at a temperature of 10 ℃ or less Sb by chemical solution growth method (CBD)2S3 A light absorber was formed. Sb formed2S3 The light absorber was prepared by annealing at 330 ° C. for 30 minutes in an Ar atmosphere.
5) 전자채널형성재/홀전도성 고분자 복합층인 홀전도층의 형성 공정5) Formation process of hole conductive layer which is electron channel forming material / hole conductive polymer composite layer
상기의 광흡수층이 형성된 기판에 전자채널형성재인 PCBM( phenyl-C61-butyricacidmethylester) 10 mg과 홀전도성 고분자인 P3HT 15 mg을 1 mL 디클로로벤젠에 용해한 복합 용액을 스핀코팅하여 전자채널/홀전도성 고분자 복합층인 정공전달체 층을 형성하였다.On the substrate on which the light absorption layer is formed, an electron channel / hole conductive polymer was spin coated by a composite solution of 10 mg of PCBM (phenyl-C 61 -butyricacidmethylester) and 15 mg of P3HT, a hole conductive polymer, dissolved in 1 mL dichlorobenzene. A hole transporter layer, which is a composite layer, was formed.
7) 금속전극 코팅 공정7) Metal Electrode Coating Process
상기의 정공전달층인 전자채널형성제/홀전도성 고분자가 코팅된 기판위에 금속전극으로 Au 증착하여 광전소자를 완성하였다.The optoelectronic device was completed by Au deposition on a substrate coated with the electron channel former / hole conductive polymer, which is the hole transport layer, using a metal electrode.
제조된 태양전지의 외부 양자 효율을 측정하기 위해, 300 W 제논 램프(Xenon lamp, Newport), 분광기(monochromator, Newport cornerstone 260)) 및 멀티-미터(multi-meter, Kethley model 2002)를 사용하여 측정하였다.In order to measure the external quantum efficiency of the manufactured solar cells, measurements were made using a 300 W Xenon lamp (Newport), a spectrometer (monochromator, Newport cornerstone 260) and a multi-meter (Kethley model 2002). It was.
상기 실시예에 따른 광전소자의 외부양자효율은 도 2에 나타내었으며 전자채널 도입을 통해 홀전도성 고분자에서 빛을 흡수하여 생성된 홀-전자 쌍의 재결합이 최소화되어 전자와 홀의 분리로 생성된 전자 외부로 전자채널을 통해 금속산화물 전자전달층에 잘 전달되어 홀전도성 고분자의 흡수가 있는 영역에서 외부양자효율은 약 65 %이다. The external quantum efficiency of the optoelectronic device according to the embodiment is shown in FIG. 2, and the recombination of the hole-electron pair generated by absorbing light in the hole-conducting polymer through the introduction of the electron channel is minimized, and thus the electron outside of the electron generated by the separation of the hole. The external quantum efficiency is about 65% in the region where the hole-conducting polymer is absorbed because it is well transferred to the metal oxide electron transport layer through the furnace electron channel.
[비교예 1]Comparative Example 1
상기 실시예 1에서 전자채널인 PCBM 채널을 형성하지 않는 것을 제외하고, 실시예 1과 동일한 방법으로 광전 소자를 제작하고 성능을 평가하였다. Except not forming the PCBM channel as an electron channel in Example 1, a photoelectric device was manufactured and evaluated in the same manner as in Example 1.
상기 비교예 1에 따른 광전소자의 외부양자효율은 도 4에 나타내었으며 외부양자효율에 대한 대비, 데이터는 표 1에 기재한 바와 같이, 홀전도성 고분자의 흡수가 있는 영역에서 전자채널을 가지는 실시예 1의 65%에서 52 %로 외부양자효율이 크게 저하됨을 알 수 있다. The external quantum efficiency of the optoelectronic device according to Comparative Example 1 is shown in FIG. 4 and the contrast with respect to the external quantum efficiency, as shown in Table 1, is an embodiment having an electron channel in the region where absorption of the hole conductive polymer is present. From 65% of 1 to 52%, it can be seen that the external quantum efficiency is greatly reduced.
[실시예 2]Example 2
상기 실시예 1에서 P3HT 홀 전도성 고분자 대신 PCPDTBT 홀전도성 고분자로 바꾼 것을 제외하고 상기 실시예 1과 동일한 방법으로 광전 소자를 제작하고 외부양자효율을 실시예 1과 같이 측정하였다.Except for replacing the P3HT hole-conducting polymer instead of the P3HT hole-conducting polymer in Example 1 to prepare a photoelectric device in the same manner as in Example 1 and measured the external quantum efficiency as in Example 1.
상기 실시예에 따른 광전소자의 외부양자효율은 도 3에 나타내었으며 전자채널 도입을 통해 홀전도성 고분자에서 빛을 흡수하여 생성된 홀-전자 쌍의 재결합이 최소화되어 전자와 홀의 분리로 생성된 전자 외부로 전자채널을 통해 금속산화물 전자전달체에 잘 전달되어 광흡수체가 흡수하지 못하는 800 nm영역에서도 외부양자효율이 약 20 %를 가지고 있어 홀전달체가 홀전도 기능 외에 장파장의 태양광을 추가적으로 흡수하여 고효율화에 기여하고 있음을 보여준다.The external quantum efficiency of the optoelectronic device according to the embodiment is shown in FIG. 3, and the recombination of the hole-electron pair generated by absorbing light in the hole-conducting polymer through the introduction of the electron channel is minimized, resulting in the separation of electrons and holes. The external quantum efficiency is about 20% even in the 800 nm area where the light absorber cannot be absorbed because it is well transmitted to the metal oxide electron transporter through the electron channel, and the hole transporter absorbs long-wavelength sunlight in addition to the hole conduction function. Show your contribution.
[비교예 2]Comparative Example 2
상기 실시예 2에서 전자채널인 PCBM 채널을 형성하지 않는 것을 제외하고, 실시예 1과 동일한 방법으로 광전 소자를 제작하고 성능을 평가하였다. Except not forming the PCBM channel as an electron channel in Example 2, and fabricated a photoelectric device in the same manner as in Example 1 and evaluated the performance.
상기 비교예 2에 따른 광전소자의 외부양자효율은 도 5에 나타내었으며 외부양자효율에 대한 대비데이터는 표 1에 기재한 바와 같이, 홀전도성 고분자의 흡수가 있는 영역에서 전자채널을 가지는 실시예 2의 외부양자효율이 약 20 %인 것에서 거의 0 %로, 장파장의 태양광으로부터 추가적인 광전자를 생성하지 못하고 있음을 알 수 있다.External quantum efficiency of the optoelectronic device according to Comparative Example 2 is shown in Figure 5 and the contrast data for the external quantum efficiency is shown in Table 1, Example 2 having an electron channel in the region of the absorption of the hole conductive polymer It can be seen that the external quantum efficiency of is about 20% to almost 0%, which does not produce additional photoelectrons from long-wavelength sunlight.
상기 실시예 1 내지 2 및 비교예 1 내지 비교예 2에 따른 광전 소자의 외부양자효율의 증가는 표 1로 나타내어 요약하였으며, 금속산화물 전자전달체 표면의 일부 및 전체 또는 무기반도체 광흡수체 표면의 일부에 코팅층을 형성하는 전자채널을 도입함으로써 홀전도성 고분자에서 빛을 흡수하여 생성된 홀-전자 쌍의 재결합이 최소화되어 전자와 홀의 분리로 생성된 전자 외부로 전자채널을 통해 금속산화물 전자전달체에 잘 전달되어 홀전도성 고분자의 흡수가 있는 영역에서도 외부양자효율의 손상이 최소화 되며, 나아가 광흡수층이 흡수하지 못하는 장파장의 태양광으로부터도 추가적인 광전자의 생성이 가능함을 보여준다.The increase in the external quantum efficiency of the photoelectric device according to Examples 1 to 2 and Comparative Examples 1 to 2 is shown in Table 1, and summarized on a part of the surface of the metal oxide electron transporter and a part of the surface of the entire or inorganic semiconductor light absorber. By introducing the electron channel forming the coating layer, the recombination of the hole-electron pair generated by absorbing light in the hole-conducting polymer is minimized, and is well transmitted to the metal oxide electron transporter through the electron channel to the outside of the electron generated by the separation of the electron and the hole. The damage of external quantum efficiency is minimized even in the region where absorption of the hole-conducting polymer is possible. Furthermore, it shows that additional photoelectrons can be generated even from long wavelength sunlight that the light absorbing layer cannot absorb.
표 1. 광전 소자의 외부양자효율Table 1. External Quantum Efficiency of Optoelectronic Devices
Figure PCTKR2012008988-appb-I000001
Figure PCTKR2012008988-appb-I000001
이상과 같이 본 발명에서는 특정된 사항들과 한정된 실시예 및 도면에 의해 설명되었으나 이는 본 발명의 보다 전반적인 이해를 돕기 위해서 제공된 것일 뿐, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다. In the present invention as described above has been described by specific embodiments and limited embodiments and drawings, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, the present invention Those skilled in the art can make various modifications and variations from this description.
따라서, 본 발명의 사상은 설명된 실시예에 국한되어 정해져서는 아니 되며, 후술하는 특허 청구범위 뿐 아니라 이 특허 청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.Accordingly, the spirit of the present invention should not be limited to the described embodiments, and all of the equivalents and equivalents of the claims, as well as the appended claims, will fall within the scope of the present invention. .

Claims (10)

  1. 전자전달층, 전자전달층의 전자전달체의 표면에 형성되는 나노 반도체무기산화물로 제조되는 광흡수층 및 홀전도층을 포함하는 광전소자로서, 상기 홀전도층은 홀전도성 고분자와 홀전도층 내부에 전자채널을 형성하는 전자채널형성재를 포함하는 광전소자. An optoelectronic device comprising an electron transport layer, a light absorption layer made of a nano-semiconductor inorganic oxide formed on the surface of an electron transporter of an electron transport layer, and a hole conduction layer, wherein the hole conduction layer is formed of an electron inside a hole conductive polymer and a hole conduction layer. Optoelectronic device comprising an electron channel forming material for forming a channel.
  2. 제 1항에 있어서,The method of claim 1,
    상기 전자채널형성재는 상기 전자 전달체 표면의 부분 또는 전부에 코팅되거나 광흡수층 표면의 일부에 코팅되어 전자채널을 형성하는 광전소자. The electron channel forming material is coated on part or all of the surface of the electron carrier or a part of the surface of the light absorption layer to form an electron channel.
  3. 제 2항에 있어서,The method of claim 2,
    상기 전자채널형성재는 풀러렌유도체, Pc2Lu, Pc2Tm, TCNQ,P TCDI-Ph, TCNNQ, NTCDI, PTCDA, F16CuPc, NYCDI-C8F, DHF-6T, Pentacene, PTCDI-C8, quinodimethane, BBL, DFH-4T, DFH-5T, DFH-6T 및 PCBM에서 선택되는 어느 하나 또는 둘 이상의 것인 광전소자.The electron channel forming material is a fullerene derivative, Pc2Lu, Pc2Tm, TCNQ, P TCDI-Ph, TCNNQ, NTCDI, PTCDA, F16CuPc, NYCDI-C8F, DHF-6T, Pentacene, PTCDI-C8, quinodimethane, BBL, DFH-4T, DFH -5T, DFH-6T, and any one or two or more selected from PCBM.
  4. 제 1항에 있어서,The method of claim 1,
    상기 전자전달체는 Ti산화물, Zn산화물, In산화물, Sn산화물, W산화물, Nb산화물, Mo산화물, Mg산화물, Zr산화물, Sr산화물, Yr산화물, La산화물, V산화물, Al산화물, Y산화물, Sc산화물, Sm산화물, Ga산화물, In산화물, SrTi산화물, 상기 산화물의 복합물 및 상기 산화물과 복합물로 코팅된 무기입자에서 선택되는 어느 하나 또는 둘 이상의 것인 광전소자. The electron carriers include Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc The photoelectric device of any one or two selected from oxides, Sm oxides, Ga oxides, In oxides, SrTi oxides, composites of the oxides and inorganic particles coated with the oxides and composites.
  5. 제 1항에 있어서,The method of claim 1,
    상기 광흡수체는 CdS, CdSe, CdTe, PbS, PbSe, PbTe, Bi2S3, Bi2Se3, InP, InAs, InGaAs, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, InSb, Si, Ge, AlAs, AlSb, InCuS2, In(CuGa)Se2, Sb2S3, Sb2Se3, Sb2Te3, SnSx(1≤x≤2), NiS, CoS, FeSx(1≤x≤2), In2S3, MoS, MoSe, Cu2S, HgTe, MgSe 및 이들의 합금에서 하나 또는 둘 이상 선택된 물질The light absorber is CdS, CdSe, CdTe, PbS, PbSe, PbTe, Bi 2 S 3 , Bi 2 Se 3 , InP, InAs, InGaAs, ZnSe, ZnTe, GaN, GaP, GaAs, GaSb, InSb, Si, Ge, AlAs, AlSb, InCuS 2 , In (CuGa) Se 2 , Sb 2 S 3 , Sb 2 Se 3 , Sb 2 Te 3 , SnS x (1≤x≤2), NiS, CoS, FeS x (1≤x≤ 2), In 2 S 3 , MoS, MoSe, Cu 2 S, HgTe, MgSe and one or more selected materials from their alloys
  6. 제 1항에 있어서,The method of claim 1,
    상기 홀전도성 고분자는 P3HT, MDMO-PPV, MEH-PPV, P3OT, PPV, TFB, POT, PCPDTBT, PCDTBT, PTPTB, PSBTBT, P2, PBBTDPP2, PDPP-BPD2, PFPDT, PFDTBT, PSiF-DBT, APFO-15, HXS-1, PFO-PTBT, APFO-Green2, PBEHTB, PF-co-DTB, 및 PFO-SeBT에서 선택되는 하나 또는 둘 이상 물질인 광전소자.The hole conductive polymer is P3HT, MDMO-PPV, MEH-PPV, P3OT, PPV, TFB, POT, PCPDTBT, PCDTBT, PTPTB, PSBTBT, P2, PBBTDPP2, PDPP-BPD2, PFPDT, PFDTBT, PSiF-DBT, APFO-15 Optoelectronic device which is one or more materials selected from HXS-1, PFO-PTBT, APFO-Green2, PBEHTB, PF-co-DTB, and PFO-SeBT.
  7. 제 1항에 있어서,The method of claim 1,
    상기 전자채널형성재는 홀전도성 고분자 100중량부에 대하여 전자채널형성재를 1 내지 500중량부를 사용하는 광전소자The electron channel forming material is an optoelectronic device using 1 to 500 parts by weight of the electron channel forming material with respect to 100 parts by weight of the hole conductive polymer.
  8. 기판 상에 전자전달체를 코팅하는 단계, Coating an electron carrier on a substrate,
    상기 전자전달체가 코팅된 기판상에 광흡수체 또는 광흡수체 전구체를 코팅하여 광흡수층을 형성하는 단계, Forming a light absorption layer by coating a light absorber or a light absorber precursor on the electron carrier coated substrate,
    상기 광흡수층을 형성한 기판 상에 전자채널형성재와 홀전도성 고분자를 각각 또는 혼합하여 코팅하여 홀전도층을 형성하는 단계;Forming a hole conductive layer by coating an electron channel forming material and a hole conductive polymer on the substrate on which the light absorption layer is formed, or by mixing them;
    를 가지는 광전소자의 제조방법.Method for manufacturing an optoelectronic device having a.
  9. 제 8항에 있어서,The method of claim 8,
    상기 홀전도층의 전자채널형성재는 상기 전자전달체 표면의 부분 또는 전부에 코팅되거나 광흡수층 표면의 일부에 코팅되어 전자채널을 형성하는 광전소자의 제조방법The electron channel forming material of the hole conductive layer is coated on part or all of the surface of the electron carrier or on a part of the surface of the light absorbing layer to form an electron channel.
  10. 제 8항에 있어서,The method of claim 8,
    상기 전자채널형성재는 풀러렌유도체, Pc2Lu, Pc2Tm, TCNQ, PTCDI-Ph, TCNNQ, NTCDI, PTCDA, F16CuPc, NYCDI-C8F, DHF-6T, Pentacene, PTCDI-C8, quinodimethane, BBL, DFH-4T, DFH-5T, DFH-6T 및 PCBM에서 선택되는 어느 하나 또는 둘 이상의 것인 광전소자의 제조방법.The electron channel forming material is a fullerene derivative, Pc2Lu, Pc2Tm, TCNQ, PTCDI-Ph, TCNNQ, NTCDI, PTCDA, F16CuPc, NYCDI-C8F, DHF-6T, Pentacene, PTCDI-C8, quinodimethane, BBL, DFH-4T, DFH- 5T, DFH-6T and PCBM any one or two or more methods of manufacturing a photoelectric device selected from.
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