WO2012002697A2 - Photoélectrode, son procédé de fabrication, et cellule solaire à colorant la comprenant - Google Patents

Photoélectrode, son procédé de fabrication, et cellule solaire à colorant la comprenant Download PDF

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WO2012002697A2
WO2012002697A2 PCT/KR2011/004703 KR2011004703W WO2012002697A2 WO 2012002697 A2 WO2012002697 A2 WO 2012002697A2 KR 2011004703 W KR2011004703 W KR 2011004703W WO 2012002697 A2 WO2012002697 A2 WO 2012002697A2
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photoelectrode
transition metal
metal oxide
dimensional porous
porous
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PCT/KR2011/004703
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Korean (ko)
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WO2012002697A3 (fr
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문준혁
조창열
진우민
강지환
신주환
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서강대학교산학협력단
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Publication of WO2012002697A3 publication Critical patent/WO2012002697A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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 application relates to a photoelectrode, a method for manufacturing the photoelectrode, and a dye-sensitized solar cell including the photoelectrode, and more particularly, a three-dimensional porous photoelectrode having optical pores in the nanometer to micrometer range, and optical interference.
  • solar cells are devices that convert solar energy into electrical energy.
  • Solar cells produce electricity using solar energy, which is an infinite energy source, and silicon solar cells, which are already widely used in our lives, are typical.
  • dye-sensitized solar cells are being researched as next-generation solar cells.
  • the dye-sensitized solar cell is representative of the paper published by Gratzel et al. [US Patent No. 5350644].
  • the structure of the dye-sensitized solar cell is one of two electrodes. It is a photoelectrode including a substrate, and an electrolyte is filled in the space between the two electrodes.
  • the solar energy is absorbed by the dye adsorbed on the semiconductor oxide electrode to generate photoelectrons, which are conducted through the semiconductor oxide layer and transferred to the conductive transparent substrate on which the transparent electrode is formed.
  • the dye is reduced by the redox pairs contained in the electrolyte.
  • the electrons that reach the opposite electrode (relative electrode) through the external wire reduce the redox pair of the oxidized electrolyte again to complete the operation process.
  • an oxide electrode is generally used a titanium dioxide electrode having a porous mesopores, generally obtained by coating titanium dioxide nanoparticles.
  • Mesopores can increase dye adsorption by increasing the specific surface area and ultimately increase the photo-electric conversion efficiency.
  • porous titanium dioxide structures has recently been carried out not only by coating nanoparticles, but also by using a casting method.
  • the casting method forms a mold through self-assembly of surfactants and polymer nanoparticles, injects titanium dioxide, and molds. Removal to obtain a porous titanium dioxide structure [Advanced Functional Materials 2009, 19, p. 1913-1099].
  • this method has a problem in that reproducibility of pore control is inferior and a time for pore formation of a relatively long time (a few hours) is required.
  • the mesopores are not easily penetrated during electrolyte injection due to their small size, which is a problem when injecting electrolytes in the form of polymers or gels.
  • dye-sensitized solar cells contain more interfaces (semiconductor
  • the energy conversion efficiency of the dye-sensitized solar cell is proportional to the amount of electrons generated by the light absorption, in order to generate a large amount of electrons by the light absorption, the photoelectrode may increase the adsorption amount of the dye molecules. Manufacturing is required.
  • an optical electrode comprising a three-dimensional porous transition metal oxide layer with pores ranging from nanometers to micrometers can be easily manufactured by a simple process using optical interference lithography and self-assembly of colloidal particles.
  • the first aspect of the present application can provide a method of manufacturing a photoelectrode comprising:
  • Forming a three-dimensional porous photoresist pattern using optical interference lithography comprising irradiating the photoresist layer with a three-dimensional optical interference pattern;
  • the photoresist pattern and the polymer colloidal self-assembly are removed using a heat firing process to form a three-dimensional porous transition metal oxide layer including a plurality of porous transition metal oxide spherical structures.
  • the three-dimensional porous transition metal oxide layer formed by the manufacturing method includes the plurality of porous transition metal oxide spherical structures, the pores between the spherical structures are connected to each other, and the plurality of porous transition metals
  • the pores inside each of the oxide spherical structures may also be connected to each other.
  • the pores in each of the plurality of porous transition metal oxide spherical structures are adjustable by the size of the polymer colloidal particles, for example, may be mesopores, but is not limited thereto.
  • the method of manufacturing the photoelectrode may further include forming a blocking layer on the conductive transparent substrate before forming the photoresist layer, but is not limited thereto.
  • the pore size of the three-dimensional porous photoresist pattern may range from several tens of nanometers to several micrometers, but is not limited thereto.
  • the pore size of the three-dimensional porous photoresist pattern is about 10 nm to about 10 ⁇ m, or about 10 nm to about 5 ⁇ m, or about 10 nm to about 1 ⁇ m, or about 50 nm to about 10 ⁇ m. Or, but not limited to, from about 100 nm to about 10 ⁇ m.
  • the size of the polymer colloidal particles may be smaller than the size of the pores of the three-dimensional porous photoresist pattern, but is not limited thereto.
  • the three-dimensional optical interference pattern may have a simple cubic structure, a face centered cubic structure or a body centered cubic structure, but is not limited thereto.
  • the photoresist layer may include, but is not limited to, a positive type photoresist resist or a negative type photoresist.
  • the forming of the 3D porous photoresist pattern may include, but is not limited to, a post-exposure baking and development process.
  • the size of the pores of the three-dimensional porous photoresist pattern may be controlled by the irradiation time of the three-dimensional optical interference pattern, but is not limited thereto.
  • the pore size of the three-dimensional porous photoresist pattern may be controlled by the post-exposure baking time, but is not limited thereto.
  • the transition metal oxide precursor is Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga and It may be to include a compound of the transition metal selected from the group consisting of a combination thereof, but is not limited thereto.
  • the polymer colloidal particles may include polystyrene (PS), polymethyl methacrylate (Poly (methyl methacrylate); PMMA], polystyrene / poly divinylbenzene (PS / DVB), polyamide, poly (butylmethacrylate-divinylbenzene) [poly (butylmethacrylate) -divinylbenzene; PBMA] and combinations thereof, but is not limited thereto.
  • PS polystyrene
  • Poly (methyl methacrylate); PMMA] polystyrene / poly divinylbenzene (PS / DVB)
  • polyamide poly (butylmethacrylate-divinylbenzene) [poly (butylmethacrylate) -divinylbenzene; PBMA] and combinations thereof, but is not limited thereto.
  • the forming of the polymer colloidal self-assembly may be performed by a process including coating a solution in which the polymer colloidal particles are dispersed in the three-dimensional porous photoresist pattern. It is not limited.
  • the coating of the solution in which the polymer colloidal particles are dispersed may be performed by spin coating, but is not limited thereto.
  • the size of the polymer colloidal self-assembly may be controlled by controlling the speed of the spin coating or by adjusting the amount of the polymer colloidal solution used when the casting method is performed, but is not limited thereto.
  • the polymer colloidal self-assembly may be formed by spin coating three or more times at 3000 RPM for colloidal particles having a size of about 100 nm to about 200 nm and 2000 RPM for colloidal particles having a size of 100 nm.
  • the heating firing is carried out at a temperature sufficient to convert the transition metal oxide precursor used to its corresponding oxide, which firing temperature is, for example, about 400 ° C. to about 600 ° C. It may be carried out at a temperature, but is not limited to this, those skilled in the art can be appropriately selected.
  • the size of each of the porous transition metal oxide spherical structure may be adjusted according to the size of the polymer colloidal particles used, but is not limited thereto.
  • the size of the polymer colloidal particles may be about 10 nm to about 300 nm, in which case the pores contained in each of the porous transition metal oxide spherical structure obtained is about 10 nm the same as the size of the polymer colloidal particles And may range in size from about 300 nm or about the same.
  • a portion of the pores included in each of the porous transition metal oxide spherical structures is about 10% or less or about 5% less than the size of the polymer colloidal particles due to slight volume shrinkage by the heat firing process. It may have a size as small as below, but is not limited thereto.
  • the method of manufacturing the photoelectrode, before inserting the polymer colloidal particles in the pores of the three-dimensional porous photoresist pattern, to modify the pore surface of the three-dimensional porous photoresist pattern to hydrophilic may be additionally included, but is not limited thereto.
  • the method of manufacturing the photoelectrode may further include adsorbing a photosensitive dye on the three-dimensional porous transition metal oxide layer, but is not limited thereto.
  • a second aspect of the present disclosure a conductive transparent substrate; And a three-dimensional porous transition metal oxide layer including a plurality of porous transition metal oxide spherical structures formed on the conductive transparent substrate.
  • pores between the plurality of porous transition metal oxide spherical structures are connected to each other, and pores inside each of the spherical structures may be connected to each other, but are not limited thereto.
  • it may further include a blocking layer formed between the conductive transparent substrate and the three-dimensional porous transition metal oxide layer, but is not limited thereto.
  • the plurality of porous transition metal oxide spherical structure may be arranged in a simple cubic structure, a face centered cubic structure or a body centered cubic structure, but is not limited thereto.
  • the size of each of the porous transition metal oxide spherical structure may be adjusted according to the size of the polymer colloidal particles used, but is not limited thereto.
  • the size of the polymer colloidal particles may be about 10 nm to about 300 nm, in which case the pores contained in each of the porous transition metal oxide spherical structure obtained is about 10 nm the same as the size of the polymer colloidal particles And may range in size from about 300 nm or about the same.
  • the transition metal oxide is Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga and these It may be to include an oxide of the transition metal selected from the group consisting of, but is not limited thereto.
  • the photoelectrode may further include a photosensitive dye adsorbed on the 3D porous transition metal oxide layer, but is not limited thereto.
  • a third aspect of the present application may provide a dye-sensitized solar cell including the photoelectrode, a counter electrode facing the photoelectrode, and an electrolyte positioned between the photoelectrode and the counter electrode.
  • a fourth aspect of the present application the photoelectrode according to the manufacturing method of the photoelectrode
  • It can provide a method for producing a dye-sensitized solar cell.
  • the present invention comprises a porous transition metal oxide layer having a three-dimensional pore structure having a variety of pores and the pores are connected to each other through a process using three-dimensional optical interference lithography and polymer colloid self-assembly
  • the photoelectrode can be easily manufactured in a short time.
  • This photoelectrode can be effectively used as a photovoltaic cell for a solar cell by increasing its specific surface area and having pores of various sizes.
  • the photoelectrode can be efficiently used as a photoelectrode for a dye-sensitized solar cell by adsorbing a dye to the photoelectrode. Can be.
  • an optimized photoelectrode is manufactured.
  • such a photoelectrode can be efficiently used for dye-sensitized solar cells.
  • it is possible to easily control the size of the mesopores by adjusting the size of the colloidal particles to be injected.
  • the photoelectrode forms a three-dimensional pore structure having a pore size in the range of nanometers to micrometers, so that light scattering can be induced to increase light absorption, and in particular, maximize light scattering of visible light.
  • the efficiency can be increased.
  • FIGS. 1A to 1F are schematic diagrams illustrating a method of manufacturing a photoelectrode according to an exemplary embodiment of the present application.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a photoelectrode according to an embodiment of the present application
  • FIG. 3 is a conceptual diagram of three-dimensional lithography (optical interference lithography) according to an embodiment of the present application
  • FIG. 4 is a block diagram of a dye-sensitized solar cell according to an embodiment of the present application.
  • FIG. 5 is an electron micrograph of a photoresist pattern including three-dimensional pores formed through optical interference lithography according to an embodiment of the present disclosure
  • 6a to 6c are electron micrographs showing a state in which colloidal particles penetrate and assemble into a photoresist and a photoresist pattern formed through optical interference lithography according to an embodiment of the present application,
  • 7A to 7C are electron micrographs of a titanium dioxide photoelectrode formed by using a photoresist formed through optical interference lithography and a colloidal particle assembly method using spin coating as a sacrificial layer,
  • FIG. 8 is a graph of photocurrent-voltage characteristics of a dye-sensitized solar cell including a photoelectrode formed through optical interference lithography according to an embodiment of the present disclosure.
  • a layer or member when a layer or member is located "on" with another layer or member, it is not only when a layer or member is in contact with another layer or member, but also between two layers or another member between the two members. Or when another member is present.
  • FIG. 1A to 1F are schematic diagrams of a method of manufacturing a photoelectrode according to an exemplary embodiment of the present application
  • FIG. 2 is a flowchart illustrating a method of manufacturing a photoelectrode according to an exemplary embodiment of the present application.
  • Step S200 is a step of forming a photoresist layer on the conductive transparent substrate 10.
  • a transparent electrode is deposited on a glass substrate or a transparent polymer substrate to prepare a conductive transparent substrate 10 (FIG. 1A).
  • the material of the transparent polymer substrate for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polypropylene (PP), poly Or a polyimide (PI), triacetyl cellulose (TAC), or a copolymer thereof, but is not limited thereto.
  • the transparent electrode formed on the substrate for a semiconductor electrode may be indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), zinc oxide ( zinc oxide), tin oxide, ZnO- (Ga 2 O 3 or Al 2 O 3 ), and mixtures thereof, including conductive metal oxides, more preferably conductive, transparent and SnO 2 having excellent heat resistance or ITO may be inexpensive in terms of cost, but is not limited thereto.
  • ITO indium tin oxide
  • FTO fluorine tin oxide
  • ATO antimony tin oxide
  • zinc oxide zinc oxide
  • tin oxide ZnO- (Ga 2 O 3 or Al 2 O 3 )
  • conductive metal oxides more preferably conductive, transparent and SnO 2 having excellent heat resistance or ITO may be inexpensive in terms of cost, but is not limited thereto.
  • a barrier layer (not shown) may be formed by coating an oxide on a conductive transparent substrate 10 to a predetermined thickness before forming the photoresist layer.
  • the material of the barrier layer, the number of heat treatments or conditions for forming the barrier layer, and the like can be variously modified within the scope of achieving the object of the present application.
  • the blocking layer is made of Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and combinations thereof. It may be to include an oxide of the transition metal selected from the group, but is not limited thereto.
  • the blocking layer serves to enhance adhesion between the conductive transparent substrate 10 and the porous transition metal oxide layer 20 when the photoelectrode 30 is formed.
  • the blocking layer may be formed by any one of a deposition method, an electrolysis method, and a wet method.
  • step S202 the three-dimensional interference pattern is irradiated onto the photoresist layer 12 to form a three-dimensional porous photoresist pattern. If necessary, the three-dimensional interference pattern may be further subjected to post-exposure baking and developing to form a three-dimensional porous photoresist pattern.
  • step S202 the photoresist layer 12 having a predetermined thickness is formed on the conductive transparent substrate 10 (FIG. 1B), and the three-dimensional interference pattern is irradiated onto the formed photoresist layer 12. 14 can be formed (FIG. 1C).
  • the thickness of the coated photoresist layer 12 may be adjusted according to the thickness of the photoelectrode to be manufactured, for example, may be formed to a thickness of about 10 ⁇ m to 30 ⁇ m, but is not limited thereto. It is not.
  • the photoresist may be coated on a conductive transparent substrate or on a blocking layer such as titanium dioxide coated on the conductive transparent substrate 10 by several nanometers.
  • an interference pattern made up of a plurality of parallel lights provided with an optical path difference can be irradiated to form a three-dimensional porous pattern 14 on the photoresist layer 12 by optical interference lithography.
  • the three-dimensional interference pattern formed by using four parallel lights may be irradiated to the photoresist layer 12 to form a three-dimensional porous pattern.
  • the method may be generated by dividing one parallel light into a plurality of lights, or applying one parallel light to a prism of a polyhedron.
  • a photo taken with an electron microscope of a photoresist with a three-dimensional porous pattern formed through optical interference lithography according to an embodiment of the present application is shown in FIG.
  • the pattern 14 formed on the photoresist layer 12 may have, for example, a three-dimensional photonic crystal form in which pores of the pattern are arranged in a simple cubic structure, a face centered cubic structure, or a body centered cubic structure. It is possible to form various grid structures by adjusting the angle and direction of light. Furthermore, by controlling the exposure time and post-exposure baking time of the irradiated interference light, the size of the pattern can be effectively controlled.
  • the size and connection of the pores in the pattern can be freely controlled by varying the three-dimensional optical interference lithography conditions, and can overcome the limitations of the pore control through the conventional nanoparticle array.
  • the porous structure is formed up to about several hundred nanometers has the advantage of smoothly filling the pores when applying the electrolyte, it can provide efficient pores for the penetration of high viscosity polymer or solid electrolyte.
  • An average diameter of pores formed by lithography according to an embodiment of the present disclosure may range from about 100 nm to about 10 ⁇ m, but is not limited thereto.
  • the photoresist layer 12 may be formed using various polymer photoresist solutions whose crosslinking or solubility is changed by photoreaction, and both a negative type and a positive type photoresist may be used.
  • Step S204 is a step of forming a self-assembly of the polymer colloidal particles 16 in the three-dimensional porous photoresist pattern 14 (FIG. 1D).
  • the colloidal particle 16 may use any particle that satisfies the above conditions as long as it satisfies the spherical shape and the uniformity of the particle and is vaporized when flying at high temperature.
  • the polymer colloidal particles 16 may include polystyrene (PS), polymethyl methacrylate (PMMA), polystyrene / divinylbenzene (PS / DVB).
  • Polyamides such as Nylon 6, poly (butylmethacrylate-divinylbenzene) [(poly (buthylmethacrylate-divinylbenzene; PBMA)], and combinations thereof It may be to include a polymer colloid particles 16.
  • Forming the polymer colloid self-assembly, comprising coating a solution in which the polymer colloid particles 16 are dispersed in the three-dimensional porous photoresist pattern Although not limited thereto, volatilization of a mixed solvent of water and alcohol as a solvent included in a solution in which the polymer colloidal particles 16 are dispersed.
  • a solvent may be used, and the concentration of the polymer colloid dispersed in the solution in which the polymer colloid particles 16 are dispersed may be used at a high concentration of 20% by weight or more, and thus, within a short time after application of the polymer colloid solution.
  • a high concentration of colloidal particles 16 may be added to a surfactant because the storage stability may be poor, and a barrier such as a conductive transparent substrate 10 or titanium dioxide coated with several nanometers may be used. If the surface of the substrate or the barrier layer is washed by plasma cleaning or the like before coating the polymer colloidal particles 16 on the layer, the spreadability of the polymer colloidal particles 16 may be improved.
  • the optical interference pattern After the modified change in the nature of water, it is separated from the colloidal particles 16 are dispersed in the water solvent to the peripheral pattern 14, the colloidal particles (16) are able to be infiltrating into the pores of the pattern. Assembling the colloidal particles 16 may be performed by a spin coating or casting method.
  • Step S206 is a step of injecting the transition metal oxide precursor solution 18 into the three-dimensional porous photoresist pattern (FIG. 1E).
  • the transition metal oxide precursor solution 18 may be injected into the photoresist pattern in which the three-dimensional pores are formed and dried for several minutes.
  • a transition metal oxide precursor that can cause a sol-gel reaction can be used.
  • the transition metal oxide precursor solution 18 is injected into the polymer colloidal self-assembled crystal layer, the conductive transparent substrate may be fixed in a vacuum, but is not limited thereto.
  • Step S208 is a step of forming a three-dimensional porous transition metal oxide layer 20 including a plurality of porous transition metal oxide spherical structures by removing the photoresist pattern and the polymer colloidal self-assembly using a heating predetermined process (FIG. 1f).
  • the porous structure may be formed while removing the photoresist 12.
  • the porous transition metal oxide layer 20 may be formed by sintering at a temperature of 400 ° C. or more for 10 minutes or more.
  • the transition metal oxide is selected from the group consisting of Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga and combinations thereof It may be an oxide of a transition metal, but is not limited thereto.
  • titanium dioxide may be used, and it is particularly preferable to produce titanium dioxide having anatase crystallinity by the sintering.
  • the three-dimensional porous transition metal oxide layer 20 formed by the manufacturing method includes the plurality of porous transition metal oxide spherical structures, and pores between the spherical structures are connected to each other, and the plurality of The pores inside each of the porous transition metal oxide spherical structures may also be connected to each other.
  • the porous structure can freely control the size and connection of the pores by changing the lithography conditions and the size change of the colloidal particles, and can overcome the limitation of the pore control through the arrangement of the conventional nanoparticles.
  • the porous structure is largely hundreds of nanometer pores formed by the optical interference method, there is an advantage that can fill the pores smoothly when applying the electrolyte, inserting colloidal particles having a size of several tens of nanometers to several hundred nanometers As a result, small pores may be additionally formed to increase the specific surface area of the photoelectrode.
  • the photoelectrode may be further formed by adsorbing the photosensitive dye on the porous transition metal oxide layer 20.
  • the dye may be coated by immersing the porous transition metal oxide layer formed as described above in a solution containing a dye.
  • the dye for example, is composed of a metal complex containing aluminum (Al), platinum (Pt), palladium (Pd), europium (Eu), lead (Pb), iridium (Ir), ruthenium (Ru) and the like.
  • the dye containing ruthenium for example, Ru (etc bpy) 2 (NCS) 2 CH 3 CN type can be used.
  • Dye-sensitized solar cell 1 including the photoelectrode 10 manufactured by the above method, as shown in Figure 4, the conductive transparent substrate 10 and the photosensitive dye A photoelectrode 30 including an adsorbed porous transition metal oxide layer 20; A counter electrode 60 including a conductive transparent substrate 40 and a conductive layer 50; Electrolyte 70; And, the sealing unit 80 may be included.
  • a blocking layer (not shown) may be formed between the conductive transparent substrate 10 and the porous transition metal oxide layer 20 if necessary.
  • the blocking layer may include an oxide and may serve to enhance adhesion between the conductive transparent substrate 10 and the porous transition metal oxide layer 20.
  • a plurality of dye molecules are adsorbed to the porous transition metal oxide layer 20.
  • the conductive transparent substrate 10 used in forming the photoelectrode 30 has a structure in which a conductive transparent electrode is formed on a transparent semiconductor electrode substrate.
  • a transparent glass substrate or a transparent polymer substrate having flexibility may be used as the substrate for the semiconductor electrode.
  • the material of the polymer substrate polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polycarbonate (PC), polypropylene (PP), polyimide (PI), triacetyl cellulose (TAC), or copolymers thereof, but are not limited thereto. no.
  • the semiconductor electrode substrate may be doped with a material selected from the group consisting of Ti, In, Ga or Al.
  • the transparent electrode formed on the substrate for a semiconductor electrode for example, indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), Zinc oxide, tin oxide, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , and conductive metal oxides selected from the group consisting of mixtures thereof, preferably conductive, SnO 2 having excellent transparency and heat resistance or ITO which is inexpensive in terms of cost may be included, but is not limited thereto.
  • the reason for employing the conductive transparent substrate 10 is to allow the sunlight to penetrate into the inside.
  • the meaning of the word transparent in the description of the present application includes not only the case where the light transmittance of the material is 100% but also the case where the light transmittance is high.
  • a plurality of dye molecules may be adsorbed to the porous transition metal oxide layer 20.
  • the pores of the porous transition metal oxide layer 20 may be, for example, arranged in a simple cubic structure, a face centered cubic structure, or a body centered cubic structure, but are not limited thereto. That is, the porous transition metal oxide layer 20 may be provided in a structure having a three-dimensional porosity. As the pores of the porous transition metal oxide layer 20 have a three-dimensional simple cubic structure, a face-centered cubic structure, or a body-centered cubic structure, a three-dimensional photonic crystal may be formed to expect a photoamplification effect.
  • an efficient electron transfer path is formed by the porous three-dimensional simple cubic structure, face centered cubic structure, or body centered cubic structure having a certain rule, thereby improving the photoelectric conversion efficiency of the dye-sensitized solar cell.
  • the electrical stability of the dye-sensitized solar cell is improved by providing an efficient passage for the penetration of a highly viscous polymer or solid electrolyte through the three-dimensional pores.
  • the pores included in each of the porous transition metal oxide spherical structures may have a size in the range of about 10 nm to about 300 nm or about the same as the size of the polymer colloidal particles.
  • the smaller the pore size of the porous transition metal oxide layer 20 having the three-dimensional pore structure is preferable. As the pore size of the porous transition metal oxide layer 20 decreases, the surface area increases, so that more dye molecules can be adsorbed, and when more dye molecules are adsorbed, more electrons are generated, which leads to energy conversion efficiency of the dye-sensitized solar cell. Because it is improved.
  • transition metal oxide included in the porous transition metal oxide layer 20 for example, Ti, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, It may include an oxide of a transition metal selected from the group consisting of Nb, Mg, Al, Y, Sc, Sm, Ga and combinations thereof.
  • the present invention is not limited thereto, and other kinds of transition metal oxides may be applied.
  • the porous transition metal oxide layer 20 includes titanium dioxide, it is preferable to use such titanium dioxide having an anatase crystallinity with good electron transfer ability.
  • a dye is adsorbed on the surface of the transition metal oxide (particle) constituting the porous transition metal oxide layer 20, electrons are generated when light is incident on and absorbed by the dye molecule, and the generated electron is the porous transition metal oxide layer 20. Is transmitted to the conductive transparent substrate 10 through the passage.
  • the counter electrode 60 is disposed to face the photoelectrode 30.
  • the counter electrode 60 may include a conductive transparent substrate 40 having a transparent electrode formed on a substrate for a semiconductor electrode, and a conductive layer 50 formed on the transparent electrode.
  • the semiconductor electrode substrate forming the counter electrode 60 may be a glass substrate or a transparent polymer substrate.
  • the transparent polymer substrate for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polypropylene (PP), polyimide (PI) ),
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • PP polypropylene
  • PI polyimide
  • the transparent electrode formed on the semiconductor electrode substrate for forming the counter electrode 60 may be indium tin oxide (ITO), fluorine tin oxide (FTO), or antimony tin oxide (antimony tin oxide).
  • ITO indium tin oxide
  • FTO fluorine tin oxide
  • antimony tin oxide antimony tin oxide
  • ATO zinc oxide
  • tin oxide ZnO-Ga 2 O 3
  • ZnO-Al 2 O 3 ZnO-Al 2 O 3
  • a mixture thereof a mixture thereof.
  • the conductive layer 50 may be formed on one surface of the counter electrode 60 disposed opposite to the porous transition metal oxide layer 20 on which the dye of the photoelectrode 30 is adsorbed.
  • the conductive layer 50 serves to activate a redox couple, and includes platinum (Pt), gold (Au), ruthenium (Ru), palladium (Pd), and rhodium (Rh). ), Iridium (Ir), osmium (Os), carbon (C), WO 3 , TiO 2 or a conductive material such as a conductive polymer.
  • the conductive layer 50 formed on one surface of the counter electrode 60 is more efficient as the reflectivity is higher, so it is better to select a material having a high reflectance.
  • An electrolyte 70 is injected between the photoelectrode 30 and the counter electrode 60.
  • the electrolyte 70 includes, for example, iodide, and serves to transfer electrons received to dye molecules that have lost electrons by receiving them from the counter electrode by oxidation and reduction.
  • the electrolyte 70 is illustrated as one layer for convenience, but may be uniformly dispersed in the pores of the photoelectrode 30.
  • the manufacturing method of the electrolyte 70 is as follows.
  • the electrolyte 70 is composed of an electrolyte, and the electrolyte is an iodide / triodide pair that receives electrons from the counter electrode 60 by oxidation and reduction and transfers the electrons to the dye molecules. do.
  • a solution in which iodine is dissolved in acetonitrile may be used as the electrolyte 70, but is not limited thereto. Any electrolyte may be used without limitation as long as it has a hole conduction function.
  • the electrolyte 70 0.7 M 1-butyl-3-methylimidazonium iodide (1-butyl-3-methylimidazolium iodide).
  • I 2 0.03 M iodine
  • 0.1 M guanidium thiocyanate 0.03 M iodine (I 2 )
  • 0.5 M 4-tert-butylpyridine were acetonitrile and valerotrile. It can be prepared by dissolving in a nitrile (valeronitrile) mixed solution (volume ratio 85: 15), but is not limited thereto.
  • Seals 80 may be formed at edges of the photoelectrode 30 and the counter electrode 60 to prevent the electrolyte 70 from leaking out.
  • the seal 80 may include a thermoplastic polymer and may be cured by heat or ultraviolet rays.
  • the sealing unit 80 may include an epoxy resin, but is not limited thereto.
  • a polymer film having a thickness of several tens of microns may be sandwiched between two electrodes of the photoelectrode 30 and the counter electrode 60 to maintain a gap.
  • a conductive transparent electrode was formed on the glass substrate to form a conductive transparent substrate.
  • a blocking layer including titanium dioxide was formed on the conductive transparent substrate. Specifically, it was formed by spin coating a 0.1 M TiCl 4 aqueous solution on a conductive transparent substrate.
  • a photoelectrode was formed on the blocking layer and the dye molecules were adsorbed.
  • the photoelectrode has a structure in which the pattern is reversed by optical interference lithography in which colloidal particles are inserted, and is formed porous.
  • the average diameter of the pores formed by lithography was in the range of more than 100 nm to 10 ⁇ m or less, and the diameter of the pores formed by the colloidal particles was in the range of 20 nm to 300 nm or less.
  • a negative photoresist SU-8 is applied and spin coating is applied at this time, so that the thickness can be controlled by several tens of micrometers depending on the RPM to allow 2000 RPM on the blocking layer. After application, spin coating was performed twice, and SU-8 was applied to have a thickness of 8 ⁇ m. Then, after heat treatment on a 95 °C hot plate (hot plate) for 3 minutes, the laser of 488 nm wavelength was refracted in a trapezoid-shaped prism having a slope, and the three-dimensional optical interference pattern was irradiated for 1 second.
  • the post-expose baking process was performed on a 95 ° C hotplate, and then dissolved by removing an uncrosslinked portion of the SU-8 photoresist using an organic solvent, and impurities were removed using 2-propanol. Washed out to form an optical interference lithography pattern (FIG. 5).
  • Penetration of the colloidal particles in the pores of the optical interference lithography pattern was used by the spin coating method.
  • Polystyrene particles were used as colloidal particles, and colloidal particles having diameters of 60 nm, 80 nm, and 110 nm were used, respectively.
  • Colloidal particles were dropped in the pattern of optical interference lithography to penetrate the colloid into the pattern.
  • 6A to 6C are electron microscope surface photographs showing a state in which a photoresist formed by optical interference lithography and a colloidal particle are assembled into the photoresist pattern. 6A to 6C, the diameters of the colloidal particles were 60 nm, 80 nm, and 110 nm, respectively.
  • a titanium dioxide precursor was injected into the photoresist pattern into which the colloidal particles were injected.
  • the titanium dioxide precursor was used as a solution or a precursor diluted in a solvent capable of causing a sol-gel reaction. Specifically, 1 M aqueous titanium tetrachloride (TiCl 4 ) solution using ethanol and water as a solvent as the titanium dioxide precursor. was used.
  • a baking process at 500 ° C. was performed for 1 hour to form a photoelectrode including a porous titanium dioxide layer by removing the photoresist pattern into which the colloidal particles were injected.
  • N719 dye a ruthenium-based dye molecule
  • Dyesol company a photoelectrode comprising a porous titanium dioxide layer adsorbed with dyes by dipping N719 in anhydrous ethanol and soaking the photoelectrode made by lithography at a concentration of 0.5 mM for one day to adsorb the dye, followed by washing and drying.
  • 7A to 7C are electron micrographs of a photoelectrode including a porous titanium dioxide layer by removing the photoresist pattern and the colloidal self-assembled layer.
  • the three-dimensional porous titanium dioxide layer formed by the manufacturing method includes a plurality of porous titanium dioxide spherical structures, the pores between the spherical structures are connected to each other, and each of the plurality of porous titanium dioxide spherical structures The pores are also connected to each other inside. 7A to 7C, the diameters of pores in the plurality of porous titanium dioxide spherical structures were about 60 nm, 80 nm, and 110 nm, respectively.
  • the counter electrode disposed in parallel to the conductive transparent substrate was formed by forming a transparent electrode on the glass substrate, a platinum layer to prepare a counter electrode.
  • the platinum layer was formed by applying a chloroplatinic acid (H 2 PtCl 6 ) solution to a conductive transparent substrate using a brush, placing the plate on a 130 ° C. hot plate, and evaporating the solvent, and performing a heat treatment at 450 ° C. for 30 minutes. To form a counter electrode.
  • a chloroplatinic acid H 2 PtCl 6
  • the electrolyte is a liquid electrolyte having an iodine-based redox pair, which is 0.1 M of lithium iodide, 0.05 M of Iodine, and 0.5 M of 4-tertbutylpyridine; TBP ) was used after dissolving in acetonitrile, and 25 ⁇ m thick Surlyn was used as a seal to prevent leakage of the electrolyte solution.
  • the dye-sensitized solar cell manufactured according to the above example was measured for current density (Jsc), voltage (Voc), filling factor (FF) and energy conversion efficiency (EFF.) At AM 1.5 and 100 mW / cm 2. The results are shown in FIG. 8 and Table 1 below.
  • the photocurrent-voltage characteristics of the dye-sensitized solar cell including the photoelectrode manufactured by using the porous titanium dioxide layer formed by the three-dimensional optical interference lithography and colloidal particle self-assembly according to the present application is shown in FIG.

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  • Microelectronics & Electronic Packaging (AREA)
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  • Photovoltaic Devices (AREA)

Abstract

La présente invention porte sur une photoélectrode, sur son procédé de fabrication et sur une cellule solaire à colorant la comprenant. La présente invention porte sur une photoélectrode poreuse tridimensionnelle dans laquelle des pores de taille nanométrique à micrométrique sont reliés les uns aux autres, sur un procédé de fabrication de la photoélectrode utilisant la lithographie interférentielle et l'auto-assemblage de particules colloïdales, et sur une cellule solaire à colorant comprenant la photoélectrode.
PCT/KR2011/004703 2010-06-29 2011-06-28 Photoélectrode, son procédé de fabrication, et cellule solaire à colorant la comprenant WO2012002697A2 (fr)

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KR101531536B1 (ko) * 2012-09-12 2015-07-07 한국화학연구원 형상 및 다공성이 제어된 상부 광활성 층을 가진 무／유기 하이브리드 태양전지 제조방법
KR101582318B1 (ko) * 2014-10-10 2016-01-06 서강대학교산학협력단 광결정 구조의 제조방법
US9733467B2 (en) 2014-12-03 2017-08-15 Hyundai Motor Company Smart glass using guided self-assembled photonic crystal
KR101634620B1 (ko) * 2015-03-27 2016-06-30 재단법인대구경북과학기술원 기공을 포함하는 금속 산화물 광전극의 제조방법, 이에 따라 제조되는 금속 산화물 광전극 및 이를 포함하는 페로브스카이트 태양전지
KR20220159262A (ko) 2021-05-25 2022-12-02 (주)티엠텍 무계목 강관 제조장치
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