WO2013002517A2 - Dispositif photoélectrique excité par semiconducteur inorganique - Google Patents

Dispositif photoélectrique excité par semiconducteur inorganique Download PDF

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WO2013002517A2
WO2013002517A2 PCT/KR2012/004949 KR2012004949W WO2013002517A2 WO 2013002517 A2 WO2013002517 A2 WO 2013002517A2 KR 2012004949 W KR2012004949 W KR 2012004949W WO 2013002517 A2 WO2013002517 A2 WO 2013002517A2
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oxide
sulfide
layer
light absorber
polarization layer
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WO2013002517A3 (fr
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석상일
임상혁
김희중
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
    • H10K30/30—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
    • H10K30/35—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 comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • 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
    • H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
    • 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
    • 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 a structure of a high efficiency inorganic semiconductor sensitive solar cell and a method of manufacturing the same. More specifically, the dithiol-type forceps-shaped dipole polarization layer forms a partial or complete coating layer on the surface of the inorganic semiconductor, which is a light absorber, and the metal oxide, which is an electron transporter, so that a charge carrier generated in the light absorber is a metal oxide.
  • the present invention relates to an inorganic semiconductor sensitized optoelectronic device having a novel structure that helps to be effectively transferred to a layer, and to manufacture thereof.
  • Solar energy is the source of all the energy of the earth, and centuries has long used solar energy in life as pollution-free energy.
  • the solar cell refers to a device capable of converting solar energy into electrical energy, and refers to a battery that generates current-voltage by using a photovoltaic effect in which photosensitive materials absorb light to generate electrons and holes.
  • N-p diodes of inorganic compound semiconductors such as silicon or gallium arsenide (GaAs) were mainly used as semiconductors of early solar cells.
  • the dye-sensitized solar cell structure has a simple structure in which a light-absorbing dye is adsorbed on a porous photoanode on a transparent electrode film that is electrically connected to light, and then another conductive glass substrate is placed on top and filled with a liquid electrolyte. have.
  • the principle of operation of dye-sensitized solar cells is when dye molecules chemically adsorbed on the surface of porous photoanode absorb solar light, dye molecules generate electron-hole pairs, and electrons are injected into the conduction of semiconductor oxide used as porous photoanode. It is delivered 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.
  • Dyes used in dye-sensitized solar cells are chemically synthesized with various materials that can increase the efficiency of solar cells due to their good light absorption. Recently, many studies have been conducted on so-called inorganic semiconductor nanoparticles or quantum dot-sensitized solar cells using inorganic semiconductor nanoparticles instead of dyes due to problems of efficiency and stability of dyes composed of organic materials.
  • Inorganic semiconductor nanoparticles have a higher light absorption coefficient than dyes used in conventional dye-sensitized solar cells, easy to control bandgap through size control of nanoparticles, and high dipole moment.
  • the exciton is characterized by relatively easy separation of electron-hols.
  • Such inorganic semiconductor nanoparticles include lead selenide (PbSe), lead sulfide (PbS), lead telluride (PbTe), cadmium sulfide (PbS), cadmium selenide (CdSe), cadmium telluride (CdTe), and antimony sulfide (III) ) (Sb 2 S 3 ), copper sulfide (I) (Cu 2 S), and mercury tellerium (HgTe).
  • the chalcogenide-based inorganic semiconductor nanoparticles are formed on the surface of the electron transporter to generate electron-hole pairs by external light.
  • the conduction band of the inorganic semiconductor nanoparticles must be higher than the conduction band of the electron transporter, and the higher the potential difference, the greater the potential for effectively transporting the electrons.
  • An object of the present invention relates to a photoelectric device of a novel structure that can improve the efficiency by introducing a dithiol-based tongs-shaped dipole polarization layer in an inorganic semiconductor-sensitized solar cell.
  • a charge carrier generated in the light absorber is formed by forming a partial or complete coating layer of a dithiol-type forceps-shaped dipole polarization layer on the surface of the inorganic semiconductor as the light absorber and the metal oxide as the electron transporter.
  • the present invention relates to an inorganic semiconductor sensitized optoelectronic device of a novel structure that helps to be effectively transferred to a layer.
  • Inorganic semiconductor-sensitized photoelectric device has a metal oxide layer containing an electron transporter, a light absorber layer comprising an inorganic semiconductor that absorbs sunlight to generate electron-holes, and dithiol-type tong-shaped dipole polarization It is characterized by the structure of the optoelectronic device composed of a layer and a hole conductor.
  • the method of manufacturing the optoelectronic device of the present invention may be applied to any conventional method in the art, for example, coating and drying the electron transporter using a printing method on a substrate, and the electron transporter is coated. Coating, firing, and drying the precursor to form a light absorber layer on the substrate. Subsequently, it can be prepared by coating or impregnating the dipole polarization layer and the hole conductor in order.
  • the dipole polarization layer may be formed by forming an electron carrier layer, a light absorber layer, a hole conductor, and then impregnating the compound or solution forming the dipole polarization layer.
  • the dipole polarization layer may form a dithiol-type forceps-shaped dipole polarization layer on part and the entire surface of the light absorber or electron transporter by depositing the device in the dipole polarization layer solution after the metal electrode coating is finished.
  • the electron transporting layer (electron transporting layer) usually uses a metal oxide, for example titanium (Ti) oxide, zinc (Zn) oxide, indium (In) oxide, tin (Sn) oxide, tungsten (W) oxide, niobium (Nb) oxide, molybdenum (Mo) oxide, magnesium (Mg) oxide, zirconium (Zr) oxide, strontium (Sr) oxide, ytterbium (Yr) oxide, lanthanum (La) oxide, One of vanadium (V) oxide, aluminum (Al) oxide, yttrium (Y) oxide, scandium (Sc) oxide, samarium (Sm) oxide, gallium (Ga) oxide, and strontium titanium (SrTi) oxide and combinations thereof The one selected above is available.
  • a metal oxide for example titanium (Ti) oxide, zinc (Zn) oxide, indium (In) oxide, tin (Sn) oxide, tungsten (W) oxide, ni
  • the thickness of the electron transporter according to the present invention is preferably 0.5 to 5 ⁇ m, but a thickness of less than 0.5 ⁇ m may not attach a light absorber formed of a sufficient amount of an inorganic semiconductor, and thus, the efficiency of the optoelectronic device may be reduced. If the thickness exceeds 5 ⁇ m, the distance for transferring the photoelectrons generated from the light to the external circuit becomes long, thereby degrading the efficiency of the optoelectronic device.
  • the particle size of the electron transporter is preferably 5 to 500 nm, 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 particle size exceeding 500 nm per unit area Since the surface area of the electron transporter is reduced, it is difficult to attach a large amount of the light absorber, which reduces the efficiency of the optoelectronic device.
  • the electron transporter titanium (Ti) oxide, zinc (Zn) oxide, indium (In) oxide, tin (Sn) oxide, tungsten (W) oxide, niobium (Nb) oxide in order to improve the interfacial contact between the particles , Molybdenum (Mo) oxide, magnesium (Mg) oxide, zirconium (Zr) oxide, strontium (Sr) oxide, ytterbium (Yr) oxide, lanthanum (La) oxide, vananium (V) oxide, aluminum (Al)
  • the pores of the electron transporter formed of the metal oxide may be coated within a very tight range.
  • the light absorber layer of the present invention is an inorganic semiconductor 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 thus, an electron transporter and an organic hole transporter.
  • the energy band matching between each element component is excellent between the elements. Therefore, it is preferable that the semiconductor be an inorganic semiconductor capable of efficiently separating and transferring excitons generated by light.
  • a light absorber layer that absorbs sunlight and generates electron-holes may be, for example, cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), and lead sulfide (PbS).
  • CdS cadmium sulfide
  • CdSe cadmium selenide
  • CdTe cadmium telluride
  • PbS lead sulfide
  • the band gap means a difference between a conduction band and a valence band of an inorganic semiconductor material, which is a light absorber layer, and when the bandgap or particle size is small depending on the inherent properties of the material,
  • the quantum-confinement effect means a band gap changed from the intrinsic properties of the material according to the nanoparticle size.
  • the light absorber layer is physically or chemically attached to the surface of the electron carrier so that electrons generated in the light absorber layer, which is an inorganic semiconductor, are well injected into the electron carrier.
  • 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. More preferably, the particles of the inorganic semiconductor, which is a light absorber, are very densely attached to the electron transporter to reduce the direct contact of the hole conductor with the electron transporter.
  • the dithiol-based tongs-shaped dipole polarization layer may cover part and all of the surface of the metal oxide layer including the light absorber layer and the electron transporter.
  • the dipole polarization layer allows the charge carriers generated in the light absorber layer to be effectively injected into the electron carrier, thereby improving external quantum efficiency.
  • the tong-shaped dipole polarization layer is preferably a material having the following Chemical Formulas 1-3.
  • R One To R 4 are independently of each other hydrogen, substituted or unsubstituted C One ⁇ C 12 Alkyl group and substituted or unsubstituted C 3 ⁇ C 20 Selected from aryl.
  • the tong-shaped dipole polarization layer according to the present invention can be used as long as the material satisfies the above chemical structural formula.
  • 1,2-ethanedithiol (1,2-ethadithiol), 1,2-benzenedithiol, Although 1,3-benzenedithiol, 1,2-dithio-4-methylbenzene, etc. are mentioned, If it is a tong-shaped compound which has a dipole polarization of the said Formula 1-3, it will restrict especially regardless of a single molecule and a polymer. It doesn't work.
  • dithiol-based forceps-shaped dipole polarization layer of the present invention may be formed by physically or chemically bonding to the surface of the inorganic semiconductor nanoparticles and the surface of the electron transporter in the shape of forceps.
  • the hole conductor of the present invention can be any material capable of transferring holes generated from the inorganic semiconductor nanoparticles, and has a hole conductor having a higher occupied molecular orbital (HOMO) than the valence band of the inorganic semiconductor nanoparticles. Is preferably.
  • HOMO occupied molecular orbital
  • P3HT poly [3-hexylthiophene]
  • MDMO-PPV poly [2-methoxy-5- (3', 7'-dimethyloctyloxyl)]-1,4-phenylene vinylene
  • MDMO-PPV poly [2-methoxy-5- (3', 7'-dimethyloctyloxyl)]-1,4-phenylene vinylene
  • MEH-PPV poly [2-methoxy-5- (2 ''-ethylhexyloxy)-p-phenylene vinylene]
  • MEH-PPV poly [2-methoxy-5- (2 ''-ethylhexyloxy)- p-phenylene vinylene]
  • P3OT poly (3-octyl thiophene)
  • liquid form hole conductor is iodine (I - / I 3 -) , bromine (Br - / Br 3 -) , polysulfide series (Poly sulfide), cobalt (Co (II) / Co ( III)), And ferrocene / ferrocenium.
  • the present invention is formed of an inorganic semiconductor (including quantum dot nanoparticles, discontinuous layer, continuous layer) that receives electrons to generate electron-hole pairs, and forms a coating layer on the surface of the light absorber layer and part or all of the metal oxide layer. Therefore, there is provided a photoelectric device including a tong-shaped dipole polarization layer.
  • the photoelectric device according to the present invention has a tong-shaped dipole polarization layer as described above to help the charge carriers generated in the light absorber layer formed of the inorganic semiconductor to be effectively injected into the electron carrier of the metal oxide layer. Since the external quantum efficiency can be improved, there is a feature to manufacture a high efficiency optoelectronic device.
  • FIG. 1 is an example showing a cross-sectional structure of an optoelectronic device according to the present invention
  • FIG. 2 is an example showing a cross-sectional structure of a photoelectric device having a multilayer inorganic semiconductor nanoparticle layer according to the present invention
  • Example 3 is an example illustrating an external quantum efficiency graph of the photoelectric device according to Example 1;
  • Example 4 is an example showing a transmission electron micrograph of a PbS quantum dot according to Example 2,
  • Example 5 is an example illustrating an external quantum efficiency graph of an optoelectronic device according to Example 2.
  • Example 8 is an example illustrating an external quantum efficiency graph of an optoelectronic device according to Example 5;
  • Example 10 is an example of evaluating the characteristics of the near-infrared sensing device according to Example 7, a) the external quantum efficiency in the near-infrared region, b) the response characteristic of the photocurrent when the external light of 1 kH is irradiated, c) It is an example showing the photocurrent response attenuation characteristics of the sensing device according to the frequency of the incident light, and (d) the photocurrent intensity of the sensing device according to the intensity of the incident light.
  • FIG. 11 is an example illustrating an external quantum efficiency graph of the photoelectric device according to Comparative Example 1;
  • FIG. 13 is an example illustrating an external quantum efficiency graph of an optoelectronic device according to Comparative Example 3;
  • FIG. 1 illustrates an example of a cross-sectional structure of an optoelectronic device according to an embodiment of the present invention.
  • An optoelectronic device including an electron carrier 10, an inorganic semiconductor nanoparticle 11, a dipole polarization layer 12, and a hole conductor 13 is shown. It is shown.
  • 2 is an example showing a cross-sectional structure of a photoelectric device having a multilayer inorganic semiconductor nanoparticle layer according to the present invention, the electron carrier 20, the inorganic semiconductor nanoparticles 21, the dipole polarization layer 22 and the hole The structure with the conductor 23 is shown.
  • ethyl cellulose Dissolved in 10% by weight of ethyl cellulose in 10% by weight of 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 added to 5 ml per 1g TiO 2, which was then mixed by the addition of Terre pinol 5 g per 1 g TiO 2, removing ethyl alcohol by distillation under reduced pressure producing the titanium dioxide powder paste.
  • 0.5 mol of sodium sulfide and 0.2 mol of potassium chloride were prepared by dissolving in a methanol / water (7: 3 volume ratio) solution.
  • 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
  • TiO 2 titanium dioxide
  • About 50 nm thick titanium dioxide (TiO 2 ) thin films of about 50 nm thickness were prepared by spray pyrolysis on the cut and partially etched FTO substrates.
  • the spray pyrolysis was performed using a solution of titanium acetylacetonate: ethanol (1: 9v / v%), and sprayed on a FTO substrate placed on a hot plate maintained at 450 ° C. for 3 seconds and stopped for 10 seconds. The thickness was adjusted.
  • titanium dioxide (TiO 2 ) thin film of the substrate using the prepared titanium dioxide (TiO 2 ) powder paste coated by screen printing method and heat-treated at 500 °C for 30 minutes, the substrate heat-treated in 20 mM titanium tetrachloride aqueous solution After soaking for about 12 hours, the mixture was washed with deionized water and ethanol, dried and heat-treated again at 500 ° C. for 30 minutes to prepare a porous electron transporter having a specific surface area of 50 m 2 / g and a thickness of 1 ⁇ m.
  • the porous electron transport substrate on which the light absorber was formed was immersed in a 10 wt% 1,2-ethanedithiol solution diluted in ethanol for 15 hours to form a dithiol-type forceps-shaped dipole polarization layer on the surface of the light absorber or electron transporter. Dried.
  • the hole conductor layer was formed by spin-coating a poly [3-hexylthiophene] (P3HT) (15 mg / 1 mL dichlorobenzene) hole conductor solution on the substrate having the dithiol-based tongs-shaped dipole polarization layer.
  • P3HT poly [3-hexylthiophene]
  • the photovoltaic device was completed by depositing gold (Au) with a metal electrode on the hole conductor-coated substrate.
  • an artificial solar device (ORIEL class A solar simulator, Newport, model 91195A) and a source-meter (source-meter, Kethley, model 2420) were used, and EQE (external) Quantum efficiency was measured using a 300W xenon lamp (Newport), a spectrometer (monochromator, Newport cornerstone 260) and a multi-meter (Kethley model 2002).
  • the external quantum efficiency of the photoelectric device according to the embodiment is shown in FIG. 3, and by introducing a dithiol-type forceps-shaped dipole polarization layer, in the situation where the external quantum efficiency is less than 1% in the near-infrared region before introduction of the polarization layer, near infrared of 1600 nm While converting light to electrons up to the region, its conversion efficiency is very effective at over 10% at 800 nm, contributing to the increase of photoelectrons.
  • Example 1 instead of spin-coating a solution of 5 mM lead nitrate (Pb (NO 3 ) 2 ) and sodium sulfide (Ns 2 S) to form lead sulfide (PbS) nanoparticles on the porous metal oxide electron transporter, Spin-coating using 0.7 wt% of lead sulfide (PbS) quantum dots dispersed in 4.5 nm hexane prepared in advance, and spin-coating a 1 wt% 1,2-ethanedithiol solution diluted in ethanol. The process was repeated five times, except that a multilayer lead sulfide (PbS) quantum dot was formed on the electron transporter, except that the photoelectric device was manufactured in the same manner as in Example 1, and the performance was measured as in Example 1.
  • PbS lead nitrate
  • Ns 2 S sodium sulfide
  • FIG. 4 is a transmission electron micrograph of the used lead sulfide (PbS) quantum dots.
  • the external quantum efficiency of the optoelectronic device according to Example 2 is shown in FIG. 5 and shows that the external quantum efficiency is very excellent by introducing a dithiol-type forceps-shaped dipole polarization layer.
  • the external quantum efficiency when the external quantum efficiency is less than 1% in the near-infrared region before the polarization layer is introduced, the external quantum efficiency is increased to about 50% or more at 800 nm by the introduction of the polarization layer, and the light is very much transferred to the near-infrared region above 1100 nm. Shows that you are converting effectively.
  • Example 2 except that the light absorbing layer was formed on the electron transporter by using a mercury-terium (HgTe) quantum dot having an average particle diameter of 5 nm dispersed in hexane instead of a lead sulfide (PbS) quantum dot.
  • HgTe mercury-terium
  • PbS lead sulfide
  • the external quantum efficiency of the optoelectronic device according to Example 3 is shown in FIG. 6 and shows that the external quantum efficiency is very excellent by introducing a dithiol-type forceps-shaped dipole polarization layer.
  • the external quantum efficiency when the external quantum efficiency is less than 1% in the near-infrared region before the polarization layer is introduced, the external quantum efficiency increases by about 20% at 1100 nm by the introduction of the polarization layer, and the light is transferred to the near-infrared region above 1100 nm. Shows that you are converting effectively.
  • Example 1 except that the cadmium selenide (CdSe) nanoparticles were formed on the electron transporter, a photovoltaic device was manufactured in the same manner as in Example 1, and performance was measured as in Example 1.
  • CdSe cadmium selenide
  • the substrate on which the porous electron transporter is formed is immersed in 0.03 mol cadmium nitrate ethanol solution and dried, and then immersed in an ethanol solution containing 0.03 mol selenium oxide and 0.06 mol sodium borohydride (NaBH 4 ) and dried. Repeated times to prepare a CdSe light absorber nanoparticle layer.
  • the external quantum efficiency of the optoelectronic device according to Example 4 is shown in FIG. 7 and shows that the external quantum efficiency is very excellent by introducing a dithiol-type tong-shaped dipole polarization layer.
  • Example 4 the solid poly [3-hexylthiophene] (P3HT) hole conductor was changed to the liquid polysulfide prepared in Preparation Example 2, and the thickness of 60 microns instead of the gold (Au) electrode (thermal adhesive film, Surlyn , Except that it was sealed using a Pt electrode having DuPont), and a photoelectric device was manufactured in the same manner as in Example 4, and the performance was measured as in Example 1.
  • P3HT solid poly [3-hexylthiophene]
  • the external quantum efficiency of the optoelectronic device according to Example 5 is shown in FIG. 8 and shows that the external quantum efficiency is very excellent by introducing a dithiol-type forceps-shaped dipole polarization layer.
  • Example 1 In Example 1, except that 1,2-benzenedithiol was used instead of 1,2-ethanedithiol as a dithiol-type tongs-shaped dipole polarization layer, a photovoltaic device was manufactured and performed in the same manner as in Example 1. Measurement was carried out as in Example 1.
  • the external quantum efficiency of the optoelectronic device according to Example 6 is shown in FIG. 9 and shows that the external quantum efficiency is very excellent by introducing a dithiol-type forceps-shaped dipole polarization layer.
  • the performance of the photodetector was evaluated in order to use the photoelectric device manufactured in Example 1 as a photodetector for detecting near infrared rays.
  • FIG. 10 The external quantum efficiency in the near infrared region, the photocurrent response characteristic according to the frequency of the external light, the attenuation characteristic of the photocurrent according to the frequency of the external light, and the intensity of the photocurrent according to the intensity of the external light are shown in FIG. 10.
  • Fig. 10 (a) shows the external quantum efficiency in the near infrared region
  • 10 (c) shows that an area in which a photocurrent signal corresponding to an input optical signal can respond well in real time is possible up to 10 kHz, and FIG.
  • the dithiol-type tong-shaped dipole polarization layer shows a very good external quantum efficiency in the near infrared region (700 nm to 1400 nm), and has the advantage of detecting a near infrared signal of 10 KHz in the absence of an external applied voltage And, even when the external light source is weak, there is an advantage that can detect the signal of the near infrared region well.
  • Example 1 Except for not forming a dithiol-type tongs-shaped dipole polarization layer in Example 1, a photovoltaic device was manufactured in the same manner as in Example 1, and performance was evaluated.
  • the external quantum efficiency of the optoelectronic device according to Comparative Example 1 is shown in Figure 11 and the contrast data for the external quantum efficiency is shown in Table 1, Example 1 having a dithiol-type tong-shaped dipole polarization layer in all areas It can be seen that the external quantum efficiency is much lower than the device of.
  • Example 2 Except for not forming a dithiol-type tongs-shaped dipole polarization layer in Example 2, a photovoltaic device was fabricated in the same manner as in Example 2, and performance was evaluated.
  • the external quantum efficiency of the optoelectronic device according to Comparative Example 2 is shown in FIG. 12 and the contrast data for the external quantum efficiency is shown in Table 1, Example 2 having a dithiol-type tong-shaped dipole polarization layer in all areas It can be seen that the external quantum efficiency is much lower than the device of.
  • Example 3 Except for not forming a dithiol-based tongs-shaped dipole polarization layer in Example 3, a photoelectric device was manufactured and evaluated for performance in the same manner as in Example 3.
  • the external quantum efficiency of the optoelectronic device according to Comparative Example 3 is shown in FIG. 13 and the contrast data for the external quantum efficiency is shown in Table 1, Example 3 having a dithiol-type tong-shaped dipole polarization layer in all areas It can be seen that the external quantum efficiency is much lower than the device of.
  • An optoelectronic device was fabricated in the same manner as in Example 4 except that the dithiol-based tongs-shaped dipole polarization layer was not formed, and the performance thereof was evaluated.
  • the external quantum efficiency of the optoelectronic device according to Comparative Example 4 is shown in Figure 14 and the contrast data for the external quantum efficiency is shown in Table 1, Example 4 having a dithiol-type tong-shaped dipole polarization layer in all areas It can be seen that the external quantum efficiency is much lower than the device of.
  • Example 5 Except for not forming a dithiol-type tongs-shaped dipole polarization layer in Example 5, an optoelectronic device was manufactured in the same manner as in Example 5, and the performance thereof was evaluated.
  • the external quantum efficiency of the optoelectronic device according to Comparative Example 5 is shown in Figure 15 and the contrast data for the external quantum efficiency is shown in Table 1, Example 5 having a dithiol-type tong-shaped dipole polarization layer in all areas It can be seen that the external quantum efficiency is much lower than the device of.
  • Example 6 An optoelectronic device was manufactured and evaluated in the same manner as in Example 6, except that the methoxybenzenethiol coating layer, which is a dipole polarization layer instead of a dithiol-based tongs-shaped dipole polarization layer, was formed in Example 6.
  • the external quantum efficiency at 500 nm as the reference wavelength is about 5%, and the value is considerably lower than about 55% of the external quantum efficiency treated with the dipole polarization layer of Example 6, indicating that the performance is significantly reduced.
  • Example 4 An optoelectronic device was manufactured and evaluated in the same manner as in Example 4, except that the methoxybenzenethiol, which is a dipole polarization layer instead of a dithiol-type tongs-shaped dipole polarization layer, was formed in Example 4.
  • the external quantum efficiency at 500 nm at the reference wavelength is about 20%, which is half lower than the external quantum efficiency of about 40% treated with the ethanedithiol dipole polarization layer. External quantum efficiency is lower than quantum efficiency (about 28%).
  • the optoelectronic device having the dithiol-based tongs-shaped dipole polarization layer of Examples 1 to 6 has a much better external quantum efficiency than the optoelectronic device having no dithiol-based tongs-shaped dipole polarization layer of Comparative Examples 1 to 7. Can be. It can be seen that the dithiol-based tongs-shaped dipole polarization layer enables the charge carriers generated in the inorganic semiconductor light absorber layer to be effectively injected into the electron transport layer.

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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un dispositif photoélectrique qui présente une nouvelle structure assurant une haute efficacité et une production en série par l'emploi de matières premières bon marché, et qui se commercialise facilement. L'invention concerne plus particulièrement un dispositif photoélectrique qui présente une surface d'un absorbeur de lumière à semiconducteur inorganique destinée à recevoir la lumière du soleil et à générer des photoélectrons et des phototrous; et une couche de polarisation bipolaire dithiol en forme de pince destinée à former une couche de revêtement partielle ou complète sur un porteur d'électrons en oxyde métallique. L'invention se caractérise en ce qu'un dispositif photoélectrique de grande efficacité peut être effectivement fabriqué par transfert efficace d'un porteur de charge généré par l'absorbeur de lumière à semiconducteur inorganique au porteur d'électrons en oxyde métallique.
PCT/KR2012/004949 2011-06-27 2012-06-22 Dispositif photoélectrique excité par semiconducteur inorganique WO2013002517A2 (fr)

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KR1020110062524A KR101246618B1 (ko) 2011-06-27 2011-06-27 무기반도체 감응형 광전소자 및 그 제조방법
KR10-2011-0062524 2011-06-27

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SE540184C2 (en) 2016-07-29 2018-04-24 Exeger Operations Ab A light absorbing layer and a photovoltaic device including a light absorbing layer
KR20180082183A (ko) * 2017-01-10 2018-07-18 한양대학교 산학협력단 전도성 전극, 이를 포함하는 양자점 태양전지, 이를 포함하는 물 분해 수소발생장치 및 이의 제조방법
KR102327199B1 (ko) 2020-01-09 2021-11-17 주식회사 한국전자재료(케이.이.엠) 전력개폐기용 세라믹 금속 이종 접합 아크 챔버 및 그 제작 방법
KR20220062213A (ko) 2020-11-06 2022-05-16 삼성디스플레이 주식회사 반도체 나노입자, 이를 포함한 전자 장치 및 상기 반도체 나노입자의 제조 방법

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JP2002353483A (ja) * 2001-05-22 2002-12-06 Toppan Printing Co Ltd 色素増感太陽電池、及びその製造方法
KR20040056427A (ko) * 2002-12-23 2004-07-01 삼성전자주식회사 접합된 나노입자를 이용한 수광소자
KR20070082385A (ko) * 2006-02-16 2007-08-21 삼성전자주식회사 양자점 발광소자 및 그 제조방법
KR20080070662A (ko) * 2005-10-20 2008-07-30 더 리전츠 오브 더 유니버시티 오브 캘리포니아 용액으로부터 형성된 나노결정 태양 전지

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JP2002353483A (ja) * 2001-05-22 2002-12-06 Toppan Printing Co Ltd 色素増感太陽電池、及びその製造方法
KR20040056427A (ko) * 2002-12-23 2004-07-01 삼성전자주식회사 접합된 나노입자를 이용한 수광소자
KR20080070662A (ko) * 2005-10-20 2008-07-30 더 리전츠 오브 더 유니버시티 오브 캘리포니아 용액으로부터 형성된 나노결정 태양 전지
KR20070082385A (ko) * 2006-02-16 2007-08-21 삼성전자주식회사 양자점 발광소자 및 그 제조방법

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