KR20130030897A - Dye-sensitized solar cell including scattering layer containing colloid crystal, and preparing method of the same - Google Patents

Abstract

PURPOSE: A dye-sensitized solar cell including a scattering layer containing colloid crystal, and a method for preparing the same are provided to easily form the scattering layer. CONSTITUTION: A photoelectrode(200) is formed on a conductive transparent substrate(100). A scattering layer(400) is formed on the photoelectrode and includes colloidal crystal(300). A counter electrode(500) faces the scattering layer. An electrolyte-containing layer(600) is positioned between the scattering layer and the counter electrode.

Description

Dye-sensitized solar cell comprising a scattering layer containing a colloidal crystal, and a method for manufacturing the same {DYE-SENSITIZED SOLAR CELL INCLUDING SCATTERING LAYER CONTAINING COLLOID CRYSTAL

The present application relates to a dye-sensitized solar cell including a scattering layer containing a colloidal crystal, and a method for producing the dye-sensitized solar cell.

In general, a solar cell is a device that converts the light energy of the sun into electrical energy. The solar cell is a tool for producing electricity by using solar energy, which is an infinite energy source, and silicon solar cells, which are already widely used in our lives, are typical. In recent years, dye-sensitized solar cells are being researched as next generation solar cells.

Dye-sensitized solar cells are typical of those published by Gratzel et al. (See US Patent No. 5,350,644). In terms of structure, one of the two electrodes of the dye-sensitized solar cell is a photoelectrode comprising a conductive transparent substrate having a semiconductor oxide layer on which a photosensitive dye is adsorbed, and a space between the two electrodes is filled with an electrolyte.

Referring to the working principle of the dye-sensitized solar cell, photovoltaic energy is generated by the absorption of solar energy by the photosensitive dye adsorbed to the semiconductor oxide layer of the electrode, and the photoelectrons are conducted through the semiconductor oxide layer to form a conductive transparent substrate having a transparent electrode. The dye, which is transferred and loses electrons, is oxidized by the redox pair contained in the electrolyte. On the other hand, the electrons that reach the counter electrode, the opposite electrode through an external wire, complete the operation of the solar cell by reducing the oxidation / reduction pair of the oxidized electrolyte again.

In dye-sensitized solar cells, the scattering layer does not necessarily have to be included. However, when manufacturing a dye-sensitized solar cell including a scattering layer, the scattering layer reflects the light passing through the photoelectrode to be used as a light source of the photoelectrode, thereby ultimately improving the photo-electric conversion efficiency of the solar cell. It can increase.

Conventionally, in order to form a scattering layer of a dye-sensitized solar cell, TiO ₂ particles were used in a paste form, and then applied on a photoelectrode and sintered (see Korean Patent No. 10-1038987). However, when using such a method, it takes a long time to form the scattering layer, since the TiO ₂ particles are irregularly stacked in the scattering layer, the wavelength of the reflected light varies depending on the direction of light incident on the photoelectrode. There was this.

The inventors have found that by applying a method of forming a scattering layer using colloidal crystals in the production of a dye-sensitized solar cell, the manufacturing time of the dye-sensitized solar cell can be reduced while the photo-electric conversion efficiency can be improved. The discovery completed the present application.

Accordingly, the present application is to provide a dye-sensitized solar cell including a scattering layer containing a colloidal crystal, and a method of manufacturing the dye-sensitized solar cell.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

A first aspect of the present disclosure provides a dye-sensitized solar cell comprising:

A photoelectrode formed on the conductive transparent substrate and having dye adsorbed thereon;

A scattering layer formed on the photoelectrode and containing colloidal crystals;

A counter electrode facing the scattering layer; And

An electrolyte-containing layer positioned between the scattering layer and the counter electrode.

A second aspect of the present application provides a method of manufacturing a dye-sensitized solar cell comprising:

Forming a photoelectrode on which the dye is adsorbed on the conductive transparent substrate;

Forming a scattering layer containing a colloidal crystal on the photoelectrode;

Arranging a counter electrode to face the scattering layer; And

Forming an electrolyte-containing layer between the scattering layer and the counter electrode.

According to the present application, by forming a scattering layer of a dye-sensitized solar cell using a colloidal crystal formed by self-assembly of the colloidal particles, the scattering layer can be produced in a short time by an easy and economical process. have.

When the dye-sensitized solar cell including the scattering layer containing the colloidal crystal is manufactured by the present application, the wavelength of the light reflected by the scattering layer is controlled according to the size of the colloidal particles used when preparing the colloidal crystal. can do.

In addition, the colloidal crystal according to the present application may be spherical, by forming the scattering layer using the spherical colloidal crystal can control the wavelength of the light reflected by the scattering layer, further improve the scattering effect, etc. In addition, since the spherical colloidal crystals have the same structure at all angles, a highly efficient dye-sensitized solar cell having a reflection effect with respect to light having the same wavelength with respect to the entire scattering layer is formed. In the case of general photonic crystals, the structure of the photonic crystals is different depending on the viewing angle to reflect different light. However, since the colloidal crystals used for forming the scattering layer are spherical, the structure of the photonic crystals is not affected by the viewing angle. There is an effect of selectively reflecting visible light of a specific wavelength. That is, in the case of a general photon crystal, the reflection wavelength depends on the viewing angle, but in the case of the spherical colloidal crystal of the present application, the reflection wavelength does not depend on the viewing angle.

In addition, when the scattering layer formed according to the present application is included in the photoelectrode for dye-sensitized solar cell, the scattering layer serves to maintain a constant number of electrons emitted at a specific wavelength compared to the amount of light irradiated to the photoelectrode. Since it is possible to take charge of, it is possible to increase the current density of the photoelectrode as a result.

1 is a schematic diagram of a dye-sensitized solar cell including a scattering layer according to an embodiment of the present application.
2 is a flowchart illustrating a process of manufacturing a scattering layer included in a dye-sensitized solar cell according to an embodiment of the present disclosure.
3A to 3C are SEM images of the scattering layer included in the dye-sensitized solar cell according to the exemplary embodiment of the present application.
4 is a photograph in which light is reflected on a silica colloidal crystal dispersed in an alcohol in one embodiment of the present application.
5 is a graph showing the transmittance according to the wavelength of light of the silica colloidal crystal dispersed in alcohol in one embodiment of the present application.
FIG. 6 shows a dye-sensitized solar cell (example) including a scattering layer containing silica colloidal crystals and a dye-sensitized solar cell (comparative example) not including a scattering layer in one embodiment of the present application. , Is a graph showing the transmittance according to the wavelength of light.
FIG. 7 illustrates a dye-sensitized solar cell (example) including a scattering layer containing silica colloidal crystals and a dye-sensitized solar cell (comparative example) not including a scattering layer in one embodiment of the present application. , A graph showing the photocurrent-voltage (IV) characteristics.
FIG. 8 is an SEM image of spherical polymer colloidal crystals prepared using polystyrene colloidal particles in one embodiment of the present application: (a) SEM image of the spherical polymer colloidal crystals (scale bar = 500 Μm), (b) SEM picture of the spherical polymer colloidal crystals (scale bar = 50 μm), and (c) SEM picture of the surface of the spherical polymer colloidal crystals (scale bar = 3 μm).

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

A first aspect of the present disclosure provides a dye-sensitized solar cell comprising:

A photoelectrode formed on the conductive transparent substrate and having dye adsorbed thereon;

A scattering layer formed on the photoelectrode and containing colloidal crystals;

A counter electrode facing the scattering layer; And

An electrolyte-containing layer positioned between the scattering layer and the counter electrode.

According to one embodiment of the present application, the colloidal crystal may include a polymer colloidal crystal or an inorganic colloidal crystal, but is not limited thereto.

According to one embodiment of the present application, the polymer colloidal crystals are polystyrene (PS), polymethyl methacrylate (PMMA), polystyrene / divinylbenzene (PS / DVB), polyamide, poly (butyl methacrylate) (PBMA ), And polymer colloidal particles including those selected from the group consisting of combinations thereof, but are not limited thereto.

According to an embodiment of the present disclosure, the inorganic colloidal crystals include inorganic colloidal particles including one selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and combinations thereof. It may be formed by, but is not limited thereto.

According to the exemplary embodiment of the present application, the colloidal crystal may be formed by self-assembly of colloidal particles, but is not limited thereto. For example, the colloidal particles may be polystyrene (PS), polymethyl methacrylate (PMMA), polystyrene / divinylbenzene (PS / DVB), polyamide, poly (butyl methacrylate) (PBMA), and their Polymer colloidal particles including those selected from the group consisting of combinations; Inorganic colloidal particles including those selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and combinations thereof; Or combinations thereof, but is not limited thereto.

As used herein, the term "self-assembly" means that the particles that are irregularly arranged have an ordered arrangement after a simple process such as drying. For example, the colloidal particles are not uniformly dispersed in the droplets when they are contained in the droplets, but when they are dried, the colloidal particles are arranged in a compact face-centered cubic structure with no gaps between the particles. This can be explained by the "self-assembly".

According to one embodiment of the present application, the wavelength of light reflected from the scattering layer may be controlled according to the particle size of the colloid contained in the scattering layer, but is not limited thereto.

According to one embodiment of the present application, the colloidal crystal may be spherical, but is not limited thereto. By forming the scattering layer using the spherical colloidal crystal according to the present application, it is possible to further control the wavelength of light reflected by the scattering layer, scattering effect, and the like, and specifically, the spherical colloidal crystal has all angles. Since it has the same structure in, it can be produced a highly efficient dye-sensitized solar cell having a reflection effect on the light of the same wavelength for the entire region where the scattering layer is formed. In the case of general photonic crystals, the structure of the photonic crystals is different depending on the viewing angle to reflect different light. However, since the colloidal crystals used for forming the scattering layer are spherical, the structure of the photonic crystals is not affected by the viewing angle. There is an effect of selectively reflecting visible light of a specific wavelength. That is, in the case of a general photon crystal, the reflection wavelength depends on the viewing angle, but in the case of the spherical colloidal crystal of the present application, the reflection wavelength does not depend on the viewing angle.

According to one embodiment of the present application, the photoelectrode may include a mesoporous transition metal oxide structure, but is not limited thereto. For example, the mesoporous transition metal oxide structure, Ti, Cu, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga And, and may include an oxide of the transition metal selected from the group consisting of, but is not limited thereto.

According to the exemplary embodiment of the present application, the electrolyte-containing layer may include one selected from the group consisting of an electrolyte-containing electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, and combinations thereof, but is not limited thereto. .

According to the exemplary embodiment of the present application, the dye-sensitized solar cell may further include a blocking layer formed between the conductive transparent substrate and the photoelectrode, but is not limited thereto.

According to the exemplary embodiment of the present application, the colloidal crystal may have a form of photonic crystals in which the colloidal particles are constantly arranged, but is not limited thereto.

According to one embodiment of the present application, the scattering layer may be to selectively reflect light of a specific wavelength, but is not limited thereto.

According to one embodiment of the present application, the scattering layer may be to selectively transmit light of a specific wavelength, but is not limited thereto.

A second aspect of the present application provides a method of manufacturing a dye-sensitized solar cell comprising:

Forming a photoelectrode on which the dye is adsorbed on the conductive transparent substrate;

Forming a scattering layer containing a colloidal crystal on the photoelectrode;

Arranging a counter electrode to face the scattering layer; And

Forming an electrolyte-containing layer between the scattering layer and the counter electrode.

According to the exemplary embodiment of the present disclosure, the method of manufacturing the dye-sensitized solar cell may further include forming a blocking layer between the conductive transparent substrate and the photoelectrode, but is not limited thereto.

According to one embodiment of the present application, the photoelectrode may include a mesoporous transition metal oxide structure, but is not limited thereto. For example, the mesoporous transition metal oxide structure, Ti, Cu, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga And, and may include an oxide of the transition metal selected from the group consisting of, but is not limited thereto.

According to one embodiment of the present application, the photoelectrode on the conductive transparent substrate may be formed using nanoparticles of the transition metal oxide as described above, but is not limited thereto. For example, by dispersing the nanoparticles of the transition metal oxide in a suitable solvent and, if necessary, by adding a dispersant, the dispersion containing the nanoparticles is applied onto the conductive transparent substrate and dried to include a mesoporous transition metal oxide structure. The photoelectrode may be manufactured. Alternatively, the photoelectrode including a mesoporous transition metal oxide structure may be prepared by coating and drying a dispersion containing the transition metal oxide, which is not in the form of nanoparticles, on the conductive transparent substrate, but is not limited thereto. The coating method is not particularly limited, but spin coating, dip coating, doctor blade method, etc. may be used, but is not limited thereto. Thereafter, the dye may be adsorbed onto the mesoporous transition metal oxide structure using a solution containing a suitable dye to complete a photoelectrode for a dye-sensitized solar cell.

According to one embodiment of the present application, the colloidal crystal may include a polymer colloidal crystal or an inorganic colloidal crystal, but is not limited thereto.

According to one embodiment of the present application, the polymer colloidal crystals are polystyrene (PS), polymethyl methacrylate (PMMA), polystyrene / divinylbenzene (PS / DVB), polyamide, poly (butyl methacrylate) (PBMA ), And polymer colloidal particles including those selected from the group consisting of combinations thereof, but are not limited thereto.

According to an embodiment of the present disclosure, the inorganic colloidal crystals include inorganic colloidal particles including one selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and combinations thereof. It may be formed by, but is not limited thereto.

According to one embodiment of the present application, the step of forming a scattering layer containing a colloidal crystal on the photoelectrode may include, but is not limited to:

The colloidal particles are dispersed in water to form an aqueous colloidal solution;

Adding a surfactant and an oil to the colloidal aqueous solution to form an aqueous colloidal / oil emulsion;

Drying the colloidal aqueous solution / oil emulsion to obtain water by separating the colloidal crystals formed by removing water; And

The obtained colloidal crystals are redispersed in a solvent and coated on the photoelectrode to form the scattering layer.

According to the exemplary embodiment of the present application, the colloidal particle may include one synthesized by a sol-gel method, but is not limited thereto. For example, in the case of using inorganic colloidal particles such as silica colloidal particles that can be used as the colloidal particles, the inorganic inorganic colloidal particles may be manufactured by using a sol-gel method, and the sol-gel method is not particularly limited and sugar Methods known in the art can be used without particular limitation. In one embodiment of the present application, when using the silica colloidal particles as the inorganic colloidal particles, by a sol-gel method using a solution containing a silica precursor, such as tetraethyl orthosilicate (TEOS), alcohol, and ammonia Synthetic may be used, but is not limited thereto.

As the surfactant, for example, hypermer 2296 may be used, but is not limited thereto.

According to one embodiment of the present application, the oil may include one selected from the group consisting of alkanes having 10 or more carbon atoms, silicone oil, and combinations thereof, but is not limited thereto. As a non-limiting example of the alkanes having 10 or more carbon atoms, alkanes having 10 to 20 carbon atoms or alkanes having 15 to 20 carbon atoms may be used, but are not limited thereto. For example, the oil may include, but is not limited to, pentadecane, hexadecane, heptadecane, or octadecane.

Examples of the silicone oil include polydimethylsiloxane, poly (1,1,1-trifluoropropylmethylsiloxane) [Poly (1,1,1-trifluoropropylmethylsiloxane)], or a combination thereof. Can be used, but is not limited thereto.

According to the exemplary embodiment of the present application, the colloidal crystal may be formed by self-assembly of polymer colloidal particles generated by evaporation of water in the process of drying the colloidal aqueous solution / oil emulsion, but is not limited thereto. It doesn't happen.

According to one embodiment of the present application, the colloidal crystal may be spherical, but is not limited thereto.

According to the exemplary embodiment of the present disclosure, obtaining and separating the colloidal crystal may include, but is not limited to, separating the polymer colloidal crystal produced when the polymer colloidal aqueous solution / oil emulsion is dried.

According to one embodiment of the present application, redispersing the obtained polymer colloidal crystals in a solvent may include, but is not limited to, dispersing the obtained polymer colloidal crystals in an alcohol solvent.

According to the exemplary embodiment of the present application, the electrolyte-containing layer may include one selected from the group consisting of an electrolyte-containing electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, and combinations thereof, but is not limited thereto. .

Hereinafter, with reference to the accompanying drawings will be described embodiments and embodiments of the present application;

1 is a schematic diagram of a dye-sensitized solar cell including a scattering layer according to an embodiment of the present application. Dye-sensitized solar cell according to an embodiment of the present application shown in Figure 1, the photoelectrode 200 is formed on the conductive transparent substrate 100, the dye is adsorbed; A scattering layer 400 formed on the photoelectrode 200 and containing a colloidal crystal 300; A counter electrode 500 facing the scattering layer 400; And an electrolyte-containing layer 600 positioned between the scattering layer 400 and the counter electrode 500, but is not limited thereto.

According to the exemplary embodiment of the present application, the photoelectrode 200 formed on the conductive transparent substrate 100 may be formed using nanoparticles of the transition metal oxide as described above, but is not limited thereto. For example, the nanoparticles of the transition metal oxide may be dispersed in a suitable solvent and, if necessary, a dispersant may be added to the dispersion containing the nanoparticles on the conductive transparent substrate and dried to include a mesoporous transition metal oxide structure. The photoelectrode 200 may be manufactured. The coating method is not particularly limited, but spin coating, dip coating, doctor blade method, etc. may be used, but is not limited thereto. Thereafter, the dye may be adsorbed onto the mesoporous transition metal oxide structure using a solution containing a suitable dye to complete the photoelectrode 200 for dye-sensitized solar cell.

For example, the mesoporous transition metal oxide structure may be immersed in a solution containing a photosensitive dye to coat the photosensitive dye by adsorbing the inner and outer surfaces of the mesoporous transition metal oxide structure, for example, the pore surface. . The photosensitive dye may be used without particular limitation in the art, for example, aluminum (Al), platinum (Pt), palladium (Pd), europium (Eu), lead (Pb), iridium (Ir) Or, it may be used a dye in the form of a complex of a metal containing ruthenium (Ru), but is not limited thereto. Among these, ruthenium (Ru) can form many organometallic composites as an element belonging to the platinum group, and photosensitive dyes containing ruthenium (Ru) are often used. For example, many types of Ru (etc bpy) ₂ (NCS) ₂ CH ₃ CN are used. Where etc is (COOEt) ₂ or (COOH) ₂ which is a reactor capable of bonding with a porous membrane such as the surface of the mesoporous transition metal oxide structure. In addition, dyes including organic dyes and the like may also be used. Examples of such organic dyes include riboflavin, triphenylmethane, coumarin, porphyrin, and xanthene. ). They can be used alone or in combination with a ruthenium (Ru) composite to improve the absorption of long wavelengths of visible light, thereby further improving the photoelectric conversion efficiency. When light is incident on and absorbed by the photosensitive dye, photoelectrons are generated, and the photoelectrons are transferred to the conductive transparent substrate through the porous transition metal oxide structure.

Hereinafter, a method of manufacturing the photoelectrode 200 included in the dye-sensitized solar cell according to the embodiment of the present application will be described in more detail.

First, the conductive transparent substrate 100 is prepared. The conductive transparent substrate 100 may be used without particular limitation those known in the art. In one embodiment, the conductive transparent substrate 100 may be manufactured by depositing a conductive transparent electrode including a conductive transparent oxide or a metal on the transparent substrate, but is not limited thereto. As the transparent substrate, any material having transparency to enable incidence of external light may be used without particular limitation, and for example, a glass substrate or a transparent polymer substrate may be used. As a transparent polymer base material which can be used as the said transparent base material, For example, polypropylene (PP), polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) , Triacetyl cellulose (TAC), or a copolymer thereof may be used, but is not limited thereto. The conductive transparent electrode formed on the transparent substrate is indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), zinc oxide (ZnO), tin oxide (SnO ₂ ), ZnO- Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ , and a conductive metal oxide selected from the group consisting of a mixture thereof may be formed. For example, the conductive transparent electrode may include tin oxide (SnO ₂ ) having excellent conductivity, transparency, and heat resistance, or indium tin oxide (ITO) which is inexpensive in terms of cost, but is not limited thereto. The conductive transparent substrate 100 is intended to be used as a hierarchical porous photoelectrode by allowing light such as sunlight to pass through and be incident therein. In addition, the meaning of the word "transparent" in the specification explaining this application includes both the case where the light transmittance of a material is high as well as the case where the light transmittance is high.

Next, a blocking layer (not shown) may be formed on the substrate as necessary. The barrier layer may be formed by coating an oxide on the substrate to a predetermined thickness. The barrier layer can be formed on the substrate by coating materials known in the art by known methods. For example, the barrier layer may be formed by vapor deposition, electrolysis, or a wet process, but is not limited thereto. 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 a range capable of achieving the object of the present application. For example, the blocking layer is Ti, Cu, Zn, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and their It may include an oxide of the transition metal selected from the group consisting of a combination, but is not limited thereto. This barrier layer serves to enhance adhesion between the substrate and the mesoporous transition metal oxide structure. For example, the barrier layer may be formed by dipping the conductive transparent substrate in an aqueous 40 mM TiCl ₄ solution and leaving it in an oven at 70 ° C. for 30 minutes, but is not limited thereto.

Next, a mesoporous transition metal oxide structure is formed on the conductive transparent substrate 100 or the blocking layer. The mesoporous transition metal oxide structure may be formed by, for example, applying a transition metal oxide nanoparticle prepared by hydrothermal synthesis to the substrate or the barrier layer using a doctor blade method and then sintering. However, it is not limited thereto. For example, the transition metal oxide nanoparticles may be titanium dioxide nanoparticles, which is a solution A which is added titanium dioxide nanopowder and triton X-100 to ethyl alcohol and stirred for about 3 hours, and α- to ethyl alcohol. Terpineol and ethyl cellulose may be added and stirred for about 3 hours, and then mixed with the solution B, followed by evaporation of the ethyl alcohol using a concentrator, thereby preparing a form contained in a viscous titanium dioxide paste. It doesn't happen. The mesoporous transition metal oxide structure, Ti, Cu, 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 combinations, but is not limited thereto.

Next, the method may further include adsorbing the photosensitive dye on the formed mesoporous transition metal oxide structure. The mesoporous transition metal oxide structure on which the photosensitive dye is adsorbed may be used as a photoelectrode of a dye-sensitized solar cell. The mesoporous transition metal oxide structure according to the present invention increases the specific surface area to increase the adsorption amount of the dye, thereby contributing to enhancing the energy conversion efficiency of the solar cell when used as a photoelectrode for a dye-sensitized solar cell. For example, the mesoporous transition metal oxide structure may be immersed in a solution containing a photosensitive dye to adsorb and coat the photosensitive dye on the inner and outer surfaces of the mesoporous transition metal oxide structure. The photosensitive dye may be used without particular limitation in the art, for example, aluminum (Al), platinum (Pt), palladium (Pd), europium (Eu), lead (Pb), iridium (Ir) Or, it may be used a dye in the form of a complex of a metal containing ruthenium (Ru), but is not limited thereto. Among these, ruthenium (Ru) can form many organometallic composites as an element belonging to the platinum group, and photosensitive dyes containing ruthenium (Ru) are often used. For example, many types of Ru (etc bpy) ₂ (NCS) ₂ CH ₃ CN are used. Where etc means (COOEt) ₂ or (COOH) ₂ . In addition, dyes including organic dyes and the like may also be used. Examples of such organic dyes include riboflavin, triphenylmethane, coumarin, porphyrin, and xanthene. ). They can be used alone or in combination with a ruthenium (Ru) composite to improve the absorption of long wavelengths of visible light, thereby further improving the photoelectric conversion efficiency. When light is incident on and absorbed by the photosensitive dye, photoelectrons are generated, and the photoelectrons are transferred to the conductive transparent substrate through the mesoporous transition metal oxide structure as a passage.

The photoelectrode 200 according to the exemplary embodiment of the present disclosure may include one in which the mesoporous transition metal oxide structure according to the present disclosure is formed on the conductive transparent substrate 100, but is not limited thereto. The photoelectrode 200 according to the present application may further include a blocking layer formed between the conductive transparent substrate 100 and the mesoporous transition metal oxide structure, but is not limited thereto. The blocking layer may include an oxide, and may serve to enhance adhesion between the conductive transparent substrate 100 and the mesoporous transition metal oxide structure.

The photoelectrode 200 according to the exemplary embodiment of the present disclosure may be expressed as a "meso porous photoelectrode" by an appearance including a plurality of pores, but is not limited thereto. The photoelectrode 200 manufactured by the above method may be used in a dye-sensitized solar cell, but is not limited thereto.

Hereinafter, a method of manufacturing the scattering layer 400 included in the dye-sensitized solar cell of the present application will be described in more detail.

2 is a flowchart illustrating a process of manufacturing the scattering layer 400 included in the dye-sensitized solar cell according to the exemplary embodiment of the present application.

According to the exemplary embodiment of the present invention, the forming of the scattering layer containing the colloidal crystals on the photoelectrode includes dispersing colloidal particles in water to form an aqueous colloidal solution (S10); Adding a surfactant and an oil to the colloidal aqueous solution to form a colloidal aqueous solution / oil emulsion (S20); Drying the colloidal aqueous solution / oil emulsion to obtain water by separating the colloidal crystals formed by removing water (S30); And redispersing the obtained colloidal crystal in a solvent to form the scattering layer by applying it on the photoelectrode (S40), but is not limited thereto.

In order to perform the step of preparing the colloidal aqueous solution by dispersing the polymer colloidal particles in distilled water (S10), it can be carried out from synthesizing the colloidal particles once. According to the exemplary embodiment of the present application, the colloidal particle may include one synthesized by a sol-gel method, but is not limited thereto. For example, the colloidal particles may be synthesized by the sol-gel method, but are not limited thereto. According to one embodiment of the present application, the silica colloidal particles that may be used as the colloidal particles may be synthesized using a solution containing tetraethyl orthosilicate (TEOS), alcohol, and ammonia, but is not limited thereto. As a silica precursor for synthesizing the silica colloidal particles, tetramethoxysilane may be used in addition to the tetraethylorthosilicate (TEOS), but is not limited thereto. For example, the silica colloidal particles may be synthesized by mixing ethanol and tetraethyl orthosilicate (TEOS) to form a mixture, and then adding distilled water and aqueous ammonia solution to the mixture and stirring for several hours at room temperature. It is not limited. The colloidal particles, such as the silica colloidal particles synthesized above may be washed several times with distilled water and then dispersed in distilled water to prepare a colloidal aqueous solution.

When manufacturing a dye-sensitized solar cell comprising a scattering layer containing the colloidal crystals formed using the colloidal particles according to the present invention, the wavelength of light reflected by the scattering layer according to the size of the colloidal particles and the colloidal crystals There is an advantage that can be controlled. For example, the colloidal particles may have a size in nm unit, the colloidal crystals may have a size in μm unit, but is not limited thereto. In one embodiment of the invention, the colloidal particles are about 1 nm to about 1000 nm, about 1 nm to about 900 nm, about 1 nm to about 800 nm, about 1 nm to about 700 nm, about 1 nm to about 600 nm, about 1 nm to about 500 nm, about 1 nm to about 400 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 10 nm to about 1000 nm, About 10 nm to about 900 nm, about 10 nm to about 800 nm, about 10 nm to about 700 nm, about 10 nm to about 600 nm, about 10 nm to about 500 nm, about 10 nm to about 400 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 100 nm to about 1000 nm, about 100 nm to about 900 nm, about 100 nm to about 800 nm, about 100 nm to It may have a size of about 700 nm, about 100 nm to about 600 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, or about 100 nm to about 200 nm. However, the present invention is not limited thereto. In one embodiment of the present disclosure, the colloidal crystals are about 1 μm to about 1,000 μm, about 1 μm to about 900 μm, about 1 μm to about 800 μm, about 1 μm to about 700 μm, about 1 μm to about 600 Μm, about 1 μm to about 500 μm, about 1 μm to about 400 μm, about 1 μm to about 300 μm, about 1 μm to about 200 μm, about 1 μm to about 100 μm, about 1 μm to about 90 μm, About 1 μm to about 80 μm, about 1 μm to about 70 μm, about 1 μm to about 60 μm, about 1 μm to about 50 μm, about 1 μm to about 40 μm, about 1 μm to about 30 μm, about 1 The microparticles may have a size of about 20 μm to about 20 μm, about 1 μm to about 10 μm, or about 1 μm to about 5 μm, but are not limited thereto.

Next, the colloidal aqueous solution may be treated with a surfactant and an oil to form a colloidal aqueous solution / oil emulsion (S20).

According to one embodiment of the present application, the oil may include one selected from the group consisting of alkanes having 10 or more carbon atoms, silicone oil, and combinations thereof, but is not limited thereto. As a non-limiting example of the alkanes having 10 or more carbon atoms, alkanes having 10 to 20 carbon atoms or alkanes having 15 to 20 carbon atoms may be used, but are not limited thereto. For example, the oil may include, but is not limited to, pentadecane, hexadecane, heptadecane, or octadecane.

The forming of the colloidal aqueous solution / oil emulsion may be performed by, for example, treating the colloidal aqueous solution with hypermer 2296 as a surfactant and hexadecane as an oil, but is not limited thereto.

Next, the colloidal aqueous solution / oil emulsion may be dried to form the colloidal crystals (S30). According to the exemplary embodiment of the present application, the colloidal crystal may be formed by self-assembly of colloidal particles generated while distilled water evaporates in the process of drying the colloidal aqueous solution / oil emulsion, but is not limited thereto. It is not. In the process of drying the colloidal aqueous solution / oil emulsion, colloidal crystallization according to evaporation of water and self-assembly may be simultaneously performed, but is not limited thereto. When the colloidal particles are present in the droplets, they are present as a non-uniformly dispersed form, but during the drying process, the colloidal particles have a gap between the colloidal particles and have an ordered form of a dense face-centered cubic structure. "Can be expressed. Self-assembly may occur even by simple drying because the concentration of the particles increases as the moisture evaporates, and thus a uniform particle arrangement is obtained.

Therefore, by forming a scattering layer of a dye-sensitized solar cell using a colloidal crystal formed by self-assembly of the colloidal particles according to the present application, the scattering layer can be prepared in a short time by an easy and economical process. There is an advantage that it can.

According to the exemplary embodiment of the present application, after the forming of the colloidal crystals, the colloidal crystals may be further included, but is not limited thereto. In addition, according to one embodiment of the present application, after the step of separating the colloidal crystals may be to further include the step of dispersing the colloidal crystals in alcohol, and evaporating the alcohol, but is not limited thereto.

Finally, the colloidal crystals may be applied onto the photoelectrode to form the scattering layer (S40). For example, the colloidal crystal dispersed in ethanol may be injected into a pipette to apply the colloidal crystal onto the photoelectrode, but the present invention is not limited thereto. According to the above-described process, it is possible to form a scattering layer of the dye-sensitized solar cell.

In the scattering layer of the dye-sensitized solar cell formed according to the present application, the colloidal crystals may be in the form of photonic crystals in which colloidal particles are constantly arranged, but is not limited thereto. In addition, the scattering layer may be to selectively reflect light of a specific wavelength and selectively transmit light of a specific wavelength, but is not limited thereto.

Since the scattering layer of the dye-sensitized solar cell formed according to the present invention is composed of spherical colloidal crystals and has the same structure at all angles, the dye-sensitized solar cell has a high-efficiency dye-sensitizing effect with respect to light having the same wavelength for the entire region where the scattering layer is formed. Solar cells can be manufactured. In the case of general photonic crystals, the structure of the photonic crystals is different depending on the viewing angle to reflect different light. However, since the colloidal crystals used for forming the scattering layer are spherical, the structure of the photonic crystals is not affected by the viewing angle. There is an effect of selectively reflecting visible light of a specific wavelength. That is, in the case of a general photon crystal, the reflection wavelength depends on the viewing angle, but in the case of the colloidal crystal of the present application, the reflection wavelength does not depend on the viewing angle.

In addition, when the scattering layer formed according to the present application is included in the photoelectrode for dye-sensitized solar cell, the scattering layer serves to maintain a constant number of electrons emitted at a specific wavelength compared to the amount of light irradiated to the photoelectrode. Since it is possible to take charge of, it is possible to increase the current density of the photoelectrode as a result.

Hereinafter, a method of manufacturing the counter electrode 500 included in the dye-sensitized solar cell of the present application will be described in more detail.

Among the components of the dye-sensitized solar cell, the counter electrode 500 is disposed to face the photoelectrode 200. The counter electrode 500 may include a conductive transparent substrate 100 having a conductive transparent electrode formed on the transparent substrate for an electrode, and, optionally, a conductive layer formed on the transparent electrode.

In the counter electrode 500, the conductive transparent substrate 100 may be formed by coating or depositing a conductive transparent electrode on the transparent substrate, similarly to the conductive transparent substrate 100 used for the photoelectrode 200. . Herein, the transparent substrate may be used without particular limitation as long as it is a material having transparency to allow incidence of external light. For example, a glass substrate or a transparent polymer substrate may be used. As the material of the transparent polymer substrate, for example, polypropylene (PP), polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), triacetyl cellulose (TAC) ), Or copolymers thereof, but are not limited thereto. In addition, the conductive transparent electrode formed on the transparent substrate, indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), zinc oxide (ZnO), tin oxide (SnO ₂ ), ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ , and mixtures thereof, and conductive metal oxides selected from the group consisting of, for example, conductivity, transparency, and heat resistance It may include, but is not limited to, superior tin oxide (SnO ₂ ), or inexpensive indium tin oxide (ITO). In this case, the reason for employing the conductive transparent substrate 100 is to allow sunlight to penetrate into the inside. In addition, the meaning of the word "transparent" in the specification explaining this application includes both the case where the light transmittance of a material is high as well as the case where the light transmittance is high.

On the other hand, the conductive layer included in the counter electrode 500 serves to activate the redox couple, platinum (Pt), gold (Au), ruthenium (Ru), palladium (Pd) , Conductive materials such as rhodium (Rh), iridium (Ir), osmium (Os), carbon (C), tungsten oxide (WO ₃ ), titanium dioxide (TiO ₂ ), or conductive polymers. The conductive layer formed on one surface of the counter electrode 500 has higher efficiency as the reflectance is higher, so it is preferable to select a material having a high reflectance.

Hereinafter, a method of manufacturing the electrolyte-containing layer 600 included in the dye-sensitized solar cell of the present application will be described in more detail.

Among the components of the dye-sensitized solar cell, an electrolyte-containing layer 600 is injected between the photoelectrode 200 and the counter electrode 500 by injecting a liquid (electrolyte), a solid polymer electrolyte, or a gel polymer electrolyte containing an electrolyte. ), But is not limited thereto. The electrolyte 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 may be uniformly dispersed in the pores of the photoelectrode. The electrolyte may be composed of an electrolyte, and the electrolyte is an iodide / triodide pair, which receives electrons from the counter electrode 500 by oxidation and reduction and transfers the electrons to the dye molecules. It may include, but is not limited thereto. For example, a solution in which iodine (Iodine, I ₂ ) is dissolved in acetonitrile (ACN) may be used as the electrolyte. However, the electrolyte is not limited thereto, and any electrolyte may be used without particular limitation. For example, as the electrolyte, 0.7 M 1-butyl-3-methylimidazolium iodide (1-butyl-3-methylimidazolium iodide, BMII), 0.03 M iodine (Iodine, I ₂ ), 0.1 M guanidium thio A mixture of acetonitrile (ACN) and valenonitrile (VN) in cyanate (Guanidium thiocyanate, GSCN) and 0.5 M 4-tert-butylpyridine (4-TBP) (volume ratio 85:15) It can be dissolved in, but is not limited thereto.

In order to prevent leakage of the electrolyte included in the dye-sensitized solar cell, a seal may be formed at the edge of the photoelectrode 200 and the counter electrode 500. The seal includes a thermoplastic polymer material and is cured by heat or ultraviolet rays. As a specific example, the sealing part may include an epoxy resin, but is not limited thereto. For example, a gap between the photoelectrode 200 and the counter electrode 500 may be sandwiched between the photoelectrode 200 and the counter electrode 500 as a sealing part.

Meanwhile, electrolytes that can be used in dye-sensitized solar cells can be classified into liquid electrolytes, gel electrolytes, and solid electrolytes according to their properties. When the solar cells are manufactured using the liquid electrolyte described above, energy conversion efficiency is increased. There is an advantage, but the solvent contained in the liquid electrolyte is leaked or volatilized according to the increase in the external temperature and the sealing state of the solar cell has a disadvantage that the life of the solar cell can be reduced. In order to solve these disadvantages, the electrolyte used in the dye-sensitized solar cell of the present application may be one selected from the group consisting of a solid polymer electrolyte, a gel polymer electrolyte, and combinations thereof, but is not limited thereto. .

The gel electrolyte may, for example, an iodine-based oxidation / reduction pair _{^{(I 3 - / I -)}} ; Low volatility organic solvents; And it may be to include a polymer material, but is not limited thereto.

For example, the iodide salt for forming the iodine-based oxidation / reduction pair may include n-methylimidazolium iodine, n-ethylimidazolium iodine, 1-benzyl-2-methylimidazolium iodine, 1-ethyl 3-methylimidazolium iodine, 1-butyl-3-methylimidazolium iodine, 1-methyl-3-propylimidazolium iodine, 1-methyl-3-isopropylimidazolium iodine, 1-methyl- 3-butylimidazolium iodine, 1-methyl-3-isobutylimidazolium iodine, 1-methyl-3-s-butylimidazolium iodine, 1-methyl-3-pentylimidazolium iodine, 1-methyl 3-isopentylimidazolium iodine, 1-methyl-3-hexylimidazolium iodine, 1-methyl-3-isohexylimidazolium iodine, 1-methyl-3-actylimidazolium iodine, 1,2 -Dimethyl-3-propylimidazolium iodine, 1-ethyl-3-isopropylimidazolium iodine, 1-propyl-3-propylimidazolium iodine, and combinations thereof It may be, but is not limited thereto.

For example, the low volatility organic solvent is selected from the group consisting of methoxypropionitrile, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, gamma-butyrolactone, dimethylformamide, and combinations thereof. It may include, but is not limited to.

For example, the polymer material may be for preparing a gel electrolyte by gelling a liquid electrolyte, but is not limited thereto. For example, the polymer material is a conductive polymer, which is capable of electron transfer like a conventional liquid electrolyte, and can solve the leakage and volatilization problem, which is one of the disadvantages of the dye-sensitized solar cell including the liquid electrolyte, but is not limited thereto. It is not. For example, the polymer material included in the gel electrolyte may include one selected from the group consisting of polyethylene oxide (PEO), polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), and combinations thereof. It may be, but is not limited thereto.

For example, the ratio of the iodide salt and the polymer material to form the iodine-based oxidation / reduction pair may include one to 1: 1 to 1: 3 based on weight%, but is not limited thereto.

Hereinafter, the dye-sensitized solar cell of the present application will be described in more detail with reference to Examples, but the present application is not limited thereto.

[ Example ]

< Example  1>

A conductive transparent substrate was formed by forming a conductive ITO transparent electrode on the glass substrate. A blocking layer including titanium dioxide was formed on the conductive transparent substrate. Specifically, the barrier layer containing titanium dioxide was formed by immersing the conductive transparent substrate in TiCl ₄ aqueous solution of 0.1 M concentration and placing the conductive transparent substrate in an oven at 70 ° C. for 30 minutes.

Thereafter, a photoelectrode on which the photosensitive dye was adsorbed was formed on the blocking layer.

Slurry, that is, titanium dioxide nanoparticles were used to manufacture the photoelectrode. To prepare the titanium dioxide nanoparticles, first, titanium dioxide nanopowder (18% by weight) and triton X-100 (2% by weight) were added to 50 ml of ethyl alcohol, and the solution was stirred for 3 hours (solution 1), And 50 ml of ethyl alcohol was added α-terpineol (60 wt%) and ethyl cellulose (20 wt%), followed by preparing a solution (solution 2) stirred for 3 hours. Thereafter, the solution 1 and the solution 2 were mixed and stirred for 24 hours, and then a viscous titanium dioxide paste was prepared by evaporating ethyl alcohol using a concentrator, and the titanium dioxide nanoparticles were adjusted to a concentration of 3.6% by weight. Obtained. The obtained titanium dioxide nanoparticles were applied to a transparent conductive substrate using a doctor blade method. As the dye molecules adsorbed on the surface of the titanium dioxide constituting the photoelectrode, any one of ruthenium or coumarin-based dye molecules may be used.

Specifically, in the present embodiment, the ruthenium-based dye molecule N719 dye was purchased from Dyesol company. N719 was dispersed in anhydrous ethanol (anhydrous ethanol) to a concentration of 0.5 mM to immerse the photoelectrode for one day to adsorb the dye.

Thereafter, a scattering layer containing silica colloidal crystals was formed on the photoelectrode. The forming of the scattering layer may include dispersing silica colloidal particles in distilled water to prepare an aqueous silica colloidal solution, treating the silica colloidal aqueous solution with a surfactant and an oil to form an aqueous silica colloidal solution / oil emulsion, and the silica The colloidal aqueous solution / oil emulsion was dried to form the silica colloidal crystals, and the silica colloidal crystals were applied on the photoelectrode to form the scattering layer.

First, the silica colloidal particles were synthesized by the sol-gel method. Specifically, the silica colloid particles were mixed with 200 mL of ethanol and 8.5 mL of tetraethyl orthosilicate (TEOS) in a 300 mL flask to form a mixture, and then 18 mL of distilled water and 9 mL of aqueous ammonia solution were added to the mixture. Synthesis by stirring at room temperature for hours. The size of the silica colloidal particles thus synthesized was about 310 nm. The synthesized silica colloidal particles were washed several times with distilled water and then dispersed in distilled water to prepare an aqueous silica colloidal solution. Subsequently, the silica colloid aqueous solution was mixed with hypermer 2296 as a surfactant and hexadecane as an oil to treat 1% by weight to form an aqueous silica colloidal solution / oil emulsion. Water was evaporated in the aqueous silica colloid / oil emulsion and the colloid was dried in an oven at about 60 ° C. for 12 hours to crystallize. As the water evaporated, spherical silica colloidal crystals having a size of about 9 μm were formed by self-assembly, and the silica colloidal crystals were dispersed in ethanol. Silica colloidal crystals dispersed in the ethanol was applied to the photoelectrode using a pipette. Thereafter, the ethanol was dried to complete the scattering layer on the photoelectrode.

FIG. 3 is an SEM image of a scattering layer included in a dye-sensitized solar cell according to an embodiment of the present disclosure, and FIG. 3A illustrates a spherical silica colloidal crystal having a size of about 9 μm including silica colloidal particles having a size of about 310 nm. SEM image of the scattering layer formed by coating the silica colloidal crystal of Figure 3a on the photoelectrode, Figure 3b is an enlarged silica colloidal crystal of Figure 3a silica colloid of about 310 nm inside SEM photograph of the arrangement of the particles.

4 is a photograph in which light is reflected on a silica colloidal crystal dispersed in an alcohol in one embodiment of the present application.

FIG. 5 is a graph showing the transmittance according to the wavelength of light of a silica colloid crystal dispersed in an alcohol according to one embodiment of the present application, and about 700 nm in the case of a silica colloid crystal including silica colloid particles having a size of about 310 nm. The minimum value of transmittance at the wavelength indicates that it reflects light of about 700 nm wavelength.

FIG. 6 shows a dye-sensitized solar cell (example) including a scattering layer containing silica colloidal crystals and a dye-sensitized solar cell (comparative example) not including a scattering layer in one embodiment of the present application. As a graph showing the transmittance according to the wavelength of light, the graph shows that the light transmittance has a relatively low light transmittance.

On the other hand, the counter electrode arrange | positioned in parallel with the said conductive transparent base material was manufactured by forming a platinum layer after forming a transparent electrode on a glass base material. Specifically, the platinum layer was formed by applying a chloroplatinic acid (H ₂ PtCl ₆ ) solution to a conductive transparent substrate, placed on a hot plate at 50 ° C., and evaporating the solvent, followed by heat treatment at 450 ° C. for 30 minutes.

Subsequently, an electrolyte was injected between the photoelectrode and the counter electrode on which the platinum layer was formed. The electrolyte may also penetrate into the pores of the photoelectrode including the hierarchical porous titanium dioxide structure. The electrolyte may be prepared by mixing several components. In the present embodiment, a liquid electrolyte having an iodine-based redox pair is used. Specifically, the AN-50 electrolyte of solaronix was used as the electrolyte, and the battery was sealed by using Surlyn having a thickness of about 60 μm so as not to leak the electrolyte solution.

At the conditions of AM 1.5 and 100 mW / cm ^2, the values of current density (Jsc), voltage (Voc), filling factor (FF), and energy conversion efficiency (EFF) of the dye-sensitized solar cell according to the present example were measured. The results are shown in FIG. 7 and Table 1 below. In order to compare the efficiency of the dye-sensitized solar cell (Example) including the scattering layer containing silica colloidal crystals according to the present embodiment with the efficiency of the dye-sensitized solar cell according to the prior art, dye-sensitized without the scattering layer The data for the solar cell (comparative example) is also shown:

area Jsc ( mA Of cm ² ) Voc (V) FF Eff . (%) Comparative example 9.43 5.72 0.566 0.661 2.140 Example 9.49 8.24 0.611 0.670 3.372

In addition, in the dye-sensitized solar cell (Example) containing a scattering layer containing silica colloidal crystals, and the dye-sensitized solar cell (Comparative Example) not containing a scattering layer, the photocurrent-voltage (IV; Current density-) Voltage) characteristic is shown as a graph of FIG. Referring to FIG. 7, in the case of the dye-sensitized solar cell (example) including the scattering layer, it can be seen that the current density and the open voltage are improved.

< Example  2>

Spherical polystyrene colloidal crystals (sizes of about 50 μm to 260 μm) were prepared using polystyrene colloidal particles (size of about 300 nm) as colloidal particles.

Specifically, the polystyrene colloidal particles were synthesized by mixing 95 mL of distilled water and 9 mL of styrene in a 250 mL flask, adding a mixed solution of 0.02 g of potassium persulfate (KPS) and 5 mL of distilled water and stirring the mixture at 80 ° C. for 16 hours. It was.

The spherical polystyrene colloidal crystals were prepared in the same manner as in the preparation of silica colloidal crystals in Example 1 using the polystyrene colloidal particles. That is, the synthesized polystyrene colloidal particles were washed several times with distilled water and then dispersed in distilled water to prepare a polystyrene colloidal aqueous solution. Subsequently, the polystyrene polymer colloid dispersion aqueous solution / oil emulsion was formed by mixing hypermer 2296, which is a surfactant, and hexadecane, which is an oil, in the polystyrene polymer colloid dispersion aqueous solution to be 1% by weight. Water was evaporated in the polystyrene polymer colloid dispersion aqueous solution / oil emulsion and the polystyrene polymer colloid was dried in an oven at about 60 ° C. for 12 hours to crystallize. As a result of evaporation of water, spherical polystyrene polymer colloidal crystals were formed by self-assembly, and the polystyrene polymer colloidal crystals were dispersed in ethanol. The polystyrene polymer colloidal crystals dispersed in the ethanol were coated on the photoelectrode using a pipette. Thereafter, the ethanol was dried to complete the scattering layer on the photoelectrode.

FIG. 8 is a SEM photograph of a spherical polystyrene colloidal crystal prepared using the polystyrene colloidal particles in the present embodiment, and FIG. 8A is a SEM photograph of the spherical polystyrene colloidal crystal (scale bar = 500 µm), FIG. 8B Shows SEM pictures of the spherical polystyrene colloidal crystals (scale bar = 50 µm), and FIG. 8C shows SEM pictures (scale bar = 3 µm) of the surface of the spherical polystyrene colloidal crystals, respectively.

The spherical polystyrene colloidal crystals thus prepared can be used as scattering layers of dye-sensitized solar cells as described in Example 1 above.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

100: conductive transparent substrate
200: photoelectrode
300: colloidal crystal
400: scattering layer
500: counter electrode
600: electrolyte-containing layer

Claims (24)

A photoelectrode formed on the conductive transparent substrate and having dye adsorbed thereon;
A scattering layer formed on the photoelectrode and containing colloidal crystals;
A counter electrode facing the scattering layer; And
An electrolyte-containing layer positioned between the scattering layer and the counter electrode
Including, dye-sensitized solar cell.
The method of claim 1,
The colloidal crystal is a dye-sensitized solar cell comprising a polymer colloidal crystal or an inorganic colloidal crystal.
The method of claim 2,
The polymeric colloidal crystals are polystyrene (PS), polymethyl methacrylate (PMMA), polystyrene / divinylbenzene (PS / DVB), polyamide, poly (butyl methacrylate) (PBMA), and combinations thereof. Dye-sensitized solar cell that is formed by including a polymer colloidal particles including those selected from the group consisting of.
The method of claim 2,
The inorganic colloidal crystal is formed by including inorganic colloidal particles including one selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and combinations thereof. battery.
The method of claim 1,
The colloidal crystal is a dye-sensitized solar cell that is formed by self-assembly of the colloidal particles (self-assembly).
The method of claim 1,
The wavelength of the light reflected from the scattering layer is controlled according to the particle size of the colloidal crystals contained in the scattering layer, dye-sensitized solar cell.
The method of claim 1,
The colloidal crystals are spherical, dye-sensitized solar cell.
The method of claim 1,
The photoelectrode comprises a mesoporous transition metal oxide structure, dye-sensitized solar cell.
The method of claim 1,
Wherein the electrolyte-containing layer comprises one selected from the group consisting of an electrolyte-containing electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, and combinations thereof.
The method of claim 1,
The dye-sensitized solar cell further comprises a blocking layer formed between the conductive transparent substrate and the photoelectrode.
The method of claim 8,
The mesoporous transition metal oxide structure, Ti, Cu, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and these Dye-sensitized solar cell comprising an oxide of the transition metal selected from the group consisting of combinations.
Forming a photoelectrode on which the dye is adsorbed on the conductive transparent substrate;
Forming a scattering layer containing a colloidal crystal on the photoelectrode;
Arranging a counter electrode to face the scattering layer; And
Forming an electrolyte-containing layer between the scattering layer and the counter electrode
A method of manufacturing a dye-sensitized solar cell comprising a.
13. The method of claim 12,
The colloidal crystals will include a polymer colloidal crystal or inorganic colloidal crystals, manufacturing method of a dye-sensitized solar cell.
The method of claim 13,
The polymeric colloidal crystals are polystyrene (PS), polymethyl methacrylate (PMMA), polystyrene / divinylbenzene (PS / DVB), polyamide, poly (butyl methacrylate) (PBMA), and combinations thereof. The method of manufacturing a dye-sensitized solar cell that is formed by including a polymer colloidal particles including those selected from the group consisting of.
The method of claim 13,
The inorganic colloidal crystal is formed by including inorganic colloidal particles including one selected from the group consisting of silica (SiO ₂ ), titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and combinations thereof. Method for producing a battery.
13. The method of claim 12,
Forming a scattering layer containing a colloidal crystal on the photoelectrode,
Dispersing the colloidal particles in water to form an aqueous colloidal solution;
Adding a surfactant and an oil to the colloidal aqueous solution to form an aqueous colloidal / oil emulsion;
Drying the colloidal aqueous solution / oil emulsion to obtain water by separating the colloidal crystals formed by removing water; And
Wherein the obtained colloidal crystals are redispersed in a solvent and coated on the photoelectrode to form the scattering layer.
To include,
Method for producing dye-sensitized solar cell.
17. The method of claim 16,
The colloidal particles are synthesized by a sol-gel method, a dye-sensitized solar cell manufacturing method.
17. The method of claim 16,
Wherein the oil is selected from the group consisting of alkanes, silicone oil, and combinations thereof, a method for producing a dye-sensitized solar cell.
17. The method of claim 16,
The colloidal crystal is a method of manufacturing a dye-sensitized solar cell, which is formed by self-assembly of the colloidal particles while the water is evaporated in the process of drying the colloidal aqueous solution / oil emulsion.
13. The method of claim 12,
The colloidal crystals are spherical, the manufacturing method of the dye-sensitized solar cell.
13. The method of claim 12,
The photoelectrode comprises a mesoporous transition metal oxide structure, a dye-sensitized solar cell manufacturing method.
13. The method of claim 12,
Wherein the electrolyte-containing layer comprises one selected from the group consisting of an electrolyte-containing electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, and combinations thereof.
13. The method of claim 12,
The method of manufacturing a dye-sensitized solar cell further comprising forming a blocking layer between the conductive transparent substrate and the photoelectrode.
22. The method of claim 21,
The mesoporous transition metal oxide structure, Ti, Cu, Zr, Sr, Zn, In, Yr, La, V, Mo, W, Sn, Nb, Mg, Al, Y, Sc, Sm, Ga, and these The method of manufacturing a dye-sensitized solar cell comprising an oxide of the transition metal selected from the group consisting of combinations.

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