WO2009066848A1 - Dye-sensitized solar cells having substrate including p-n junction diode - Google Patents

Dye-sensitized solar cells having substrate including p-n junction diode Download PDF

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Publication number
WO2009066848A1
WO2009066848A1 PCT/KR2008/003687 KR2008003687W WO2009066848A1 WO 2009066848 A1 WO2009066848 A1 WO 2009066848A1 KR 2008003687 W KR2008003687 W KR 2008003687W WO 2009066848 A1 WO2009066848 A1 WO 2009066848A1
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Prior art keywords
layer
dye
sensitized solar
solar cell
junction diode
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PCT/KR2008/003687
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French (fr)
Inventor
Yong-Seok Jun
Seung-Yup Lee
Ho-Gyeong Yun
Man-Gu Kang
Jong-Dae Kim
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Electronics And Telecommunications Research Institute
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Publication of WO2009066848A1 publication Critical patent/WO2009066848A1/en

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    • 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
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    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
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    • 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
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    • 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
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Definitions

  • the present invention relates to a solar cell, and more particularly, to a dye-sensitized solar cell having a substrate including a p-n junction diode.
  • a dye-sensitized solar cell is a photoelectrochemical solar cell.
  • the main constituent elements of the dye-sensitized solar cell are photosensitive dye molecules that can generate electron-hole pairs by absorbing visible light and a transition metal oxide that transmits the generated electrons.
  • a representative example of a dye-sensitized solar cell is a dye- sensitized solar cell that includes a semiconductor electrode formed of TiO 2 nano particles to which dye molecules are adsorbed, a facing electrode coated with Pt or carbon, and an electrolyte solution filled between the semiconductor electrode and the facing electrode. This type of photochemical solar cell has received much attention due to low manufacturing costs per unit power compared to a conventional silicon solar cell.
  • a dye-sensitized solar cell is operated in the following manner. Dyes excited by sunlight inject electrons into a conduction band of TiO 2 nano particles. The injected electrons reach a conductive substrate passing through the TiO 2 nano particles, and are transmitted to an external circuit. The electrons that have done an electrical work in the external circuit are injected into the TiO 2 nano particles through the facing electrode due to an electron transmission function of the oxidation/reduction electrolyte to reduce the dyes that are deficient in electrons, thereby completing the operation of the dye-sensitized solar cell. Disclosure of Invention Technical Problem
  • a dye adsorbed in a TiO 2 layer of a semiconductor electrode generates electrons by absorbing light of a limited wavelength region of the sunlight.
  • light of other wavelength regions that are not absorbed by the dye or light that is not used for generating electricity even though the light has wavelengths that can be absorbed by the dye are not used for generating electrons. Therefore, the conventional dye-sensitized solar cell has a low energy conversion efficiency, and thus, there is a limit in efficiently using the dye-sensitized solar cell.
  • the present invention provides a dye- sensitized solar cell that can maximize energy conversion efficiency by generating electricity through absorbing a wide range of wavelengths of sunlight.
  • a dye-sensitized solar cell comprising: a semiconductor electrode formed on a first conductive substrate; a facing electrode formed on a second conductive substrate; and an electrolyte layer interposed between the semiconductor electrode and the facing electrode, wherein one of the first conductive substrate and the second conductive substrate comprises a p-n junction diode.
  • One selected from the first conductive substrate and the second conductive substrate may comprise the p-n junction diode and a conductive layer formed on the p-n junction diode.
  • the first conductive substrate may comprise: the p-n junction diode comprising a p-type semiconductor layer and an n-type semiconductor layer; and a first conductive layer formed on the p-n junction diode to contact the p-type semiconductor layer, and the semiconductor electrode may be formed to contact the first conductive layer.
  • the second conductive substrate may comprise: the p-n junction diode comprising a p-type semiconductor layer and an n-type semiconductor layer; and a second conductive layer formed on the p-n junction diode to contact the n-type semiconductor layer, and the facing electrode may be formed to contact the second conductive layer.
  • One of the first conductive substrate and the second conductive substrate may comprise: a transparent substrate; a first conductive layer formed on the transparent substrate; the p-n junction diode formed on the first conductive layer; and a second conductive layer formed on the p-n junction diode.
  • a dye- sensitized solar cell comprising: a semiconductor electrode formed on a first conductive substrate; a facing electrode formed on a second conductive substrate; and an electrolyte layer interposed between the semiconductor electrode and the facing electrode, wherein the first conductive substrate and the second conductive substrate respectively comprise a p-n junction diode.
  • the p-n junction diode may have one of a structure in which a p-type CIS compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer are sequentially stacked, and a structure in which a p-type a-Si layer, an i (intrinsic)-type a-Si layer, and an n-type a-Si layer are sequentially stacked.
  • the first conductive substrate and the second conductive substrate respectively may have p-n junction diode structures different from each other or the same p-n junction diode structure.
  • a dye-sensitized solar cell In a dye-sensitized solar cell according to the present invention, at least one of a first conductive substrate on which a semiconductor electrode is formed and a second conductive substrate on which a facing electrode is formed has a tandem structure that includes a p-n junction diode.
  • the dye-sensitized solar cell according to the present invention has a structure that can generate electricity by absorbing various lights including light that is not absorbed by the dye-sensitized solar cell or light that is not used for generating electricity in a conventional dye-sensitized solar cell. Thus, an opening voltage and the energy conversion efficiency of the dye-sensitized solar cell can be increased. Description of Drawings
  • FIG. 1 is a cross-sectional view of a dye-sensitized solar cell according to an embodiment of the present invention
  • FIG. 2 is a cross-sectional view of a dye-sensitized solar cell according to another embodiment of the present invention.
  • FIG. 3 is a cross-sectional view of a dye-sensitized solar cell according to another embodiment of the present invention.
  • FIG. 4 is a cross-sectional view of a dye-sensitized solar cell according to another embodiment of the present invention. Best Mode
  • FIG. 1 is a cross-sectional view of a dye-sensitized solar cell 100 according to an em- bodiment of the present invention.
  • the dye-sensitized solar cell 100 includes a semiconductor electrode 130 formed on a first conductive substrate 110 and a facing electrode 170 formed on a second conductive substrate 150.
  • An electrolyte layer 190 is interposed between the semiconductor electrode 130 and the facing electrode 170.
  • the first conductive substrate 110 and the second conductive substrate 150 respectively include tandem structures 120 and 160 that respectively include p-n junction diodes.
  • the first conductive substrate 110 includes a first transparent substrate 112, a first conductive layer 114, the tandem structure 120 including a p-n junction diode, and a second conductive layer 128, which are sequentially stacked.
  • the second conductive substrate 150 includes a second transparent substrate 152, a third conductive layer 154, the tandem structure 160 including a p-n junction diode, and a fourth conductive layer 168, which are sequentially stacked.
  • the first transparent substrate 112 and the second transparent substrate 152 respectively may be formed of glass or plastic.
  • the first conductive layer 114, the second conductive layer 128, the third conductive layer 154, and the fourth conductive layer 168 respectively may be formed of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), or SnO 2 .
  • the first transparent substrate 112 and the second transparent substrate 152 respectively may be a conductive transparent substrate formed of a conductive polymer. In this case, it is unnecessary to form the first conductive layer 114 and the third conductive layer 154.
  • the tandem structures 120 and 160 include p-n junction diodes that respectively include a p-type semiconductor layer and an n-type semiconductor layer.
  • the p-type semiconductor layer may be formed to contact the second conductive layer 128.
  • the semiconductor electrode 130 is formed directly above the second conductive layer 128 so as to be in contact with the second conductive layer 128. That is, in the first conductive substrate 110, the p-type semiconductor layer of the tandem structure 120 that includes the p-n junction diode is disposed to adjacent to the semiconductor electrode 130.
  • the n-type semiconductor layer may be formed to contact the fourth conductive layer 168.
  • the facing electrode 170 is formed directly above the fourth conductive layer 168 so as to be in contact with the fourth conductive layer 168. That is, in the second conductive substrate 150, the n-type semiconductor layer of the tandem structure 160 that includes the p-n junction diode is disposed to adjacent to the facing electrode 170.
  • the tandem structures 120 and 160 that include a p-n junction diode respectively may be formed in a structure in which a p-type CuInSe 2 (CIS) compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer are sequentially stacked.
  • the tandem structures 120 and 160 that include a p-n junction diode may be formed in a structure in which an n-type a-Si layer, an i-type a-Si layer, and a p-type a-Si layer are sequentially stacked.
  • the tandem structures 120 and 160 that include a p-n junction diode may have a p-n junction diode structure comprising an n-type GaAs layer and a p-type GaAs layer.
  • the first conductive layer 114 and the second conductive layer 128 may be or may not be formed of the same material.
  • the first conductive layer 114 and the second conductive layer 128 may be formed of one material or materials different from each other selected from the group consisting of FTO, ITO, Mo, SnO 2 , and Ge.
  • the semiconductor electrode 130 may be a metal oxide layer to which dye molecules are adsorbed.
  • the metal oxide layer may be formed of, for example, TiO 2 , SnO 2 , or ZnO to a thickness of 3 to 12 ⁇ m.
  • the metal oxide layer may be formed of TiO 2 particles having a size of 15 to 25nm.
  • the dye adsorbed to the metal oxide layer may be a ruthenium complex.
  • the facing electrode 170 may be formed of Pt.
  • the electrolyte layer 190 is filled in a space sealed by a sealant 180 between the semiconductor electrode 130 and the facing electrode 170.
  • the electrolyte layer 190 may be formed of an iodine group oxidation-reduction liquid electrolyte.
  • the electrolyte layer 190 may be an I 3 Vr electrolyte in which 0.6M of l-hexyl-3-dimethyl-imidazolium iodide, 0.03M of I 2 (iodine), 0.5M of t-butylpyridine, and 0. IM of guanidium thiocyanate are dissolved in a mixed solvent of acetonitrile and valeronitrile.
  • the sealant 180 may be formed of a thermoplastic polymer film such as surlyn to a thickness of 30 to 50 ⁇ m and a width of 1 to 4mm.
  • FIG. 1 depicts the structures of the first conductive substrate 110 and the second conductive substrate 150, in which the tandem structures 120 and 160 having the p-n junction diode are respectively included.
  • the tandem structures 120 and 160 having the p-n junction diode may have the same structure or may have structures different from each other. Also, one of the tandem structures 120 and 160 having the p-n junction diode may be omitted, if necessary.
  • Mode for Invention
  • FIG. 2 is a cross-sectional view of a main configuration of a dye-sensitized solar cell
  • FIG. 2 the same reference numerals as in FIG. 1 indicate like elements, and thus, the descriptions thereof will not be repeated.
  • a tandem structure 220 includes a p-n junction diode formed of amorphous silicon a-Si, and a tandem structure 260 includes a p-n junction diode formed of a CuInSe 2 (CIS) compound semiconductor.
  • CIS CuInSe 2
  • the tandem structure 220 that includes the p-n junction diode has a structure in which an n-type a-Si layer 222, an i (intrinsic) type a-Si layer 224, and a p- type a-Si layer 226 are sequentially stacked.
  • the second conductive layer 128 and the semiconductor electrode 130 are sequentially formed on the p-type a-Si layer 226.
  • the first conductive layer 114 and the second conductive layer 128 may be formed of FTO.
  • the tandem structure 220 that include the p-n junction diode has a structure in which a p-type CIS compound semiconductor layer 262, an n-type CdS layer 264, and an n- type ZnO: Al layer 266 are sequentially stacked.
  • the fourth conductive layer 168 and the facing electrode 170 are sequentially formed on the n-type ZnO:Al layer 266.
  • the third conductive layer 154 may be formed of Mo
  • the fourth conductive layer 168 may be formed of FTO.
  • the tandem structure 220 in which the n-type a-Si layer 222, the i (intrinsic)-type a-Si layer 224 and the p-type a-Si layer 226 are sequentially stacked is formed.
  • the transparent second conductive layer 128 is coated on the p-type a-Si layer 226 using FTO or ITO.
  • the semiconductor electrode 130 is formed on the second conductive layer 128.
  • a process of forming a dye molecule layer may be performed by adsorbing the dye molecules on surfaces of metal oxide particles that constitute the metal oxide semiconductor layer.
  • the tandem structure 260 is formed, in which the third conductive layer 154, the p-type CIS compound semiconductor layer 262, the n-type CdS layer 264, and the n-type ZnO:Al layer 266 are sequentially stacked on the second transparent substrate 152 .
  • the transparent fourth conductive layer 168 is formed on the an n-type ZnO: Al layer 266 using, for example, FTO or ITO.
  • the facing electrode 170 is formed on the fourth conductive layer 168.
  • the facing electrode 170 may be formed using the following process.
  • the facing electrode 170 may be formed of Pt on the fourth conductive layer 168 using a high temperature reduction method for a Pt 2+ solution. However, if the tandem structure 260 is relatively unstable at a high temperature of approximately 400 0 C, the facing electrode 170 may be formed of Pt on the fourth conductive layer 168 using a chemical reduction method.
  • the electrons transmitted to the n- type a-Si layer 222 move to holes in the p-type CIS compound semiconductor layer 262 of the second conductive substrate 150 along an external circuit (not shown), which is connected from the first conductive substrate 110 to the second conductive substrate 150. Electrons generated from the p-type CIS compound semiconductor layer 262 due to external light move to the facing electrode 170 through the n-type CdS layer 264 and the n-type ZnO:Al layer 266. The electrons moved to the facing electrode 170 are transmitted to the electrolyte layer 190, which is in an electron deficient state. The electron transmitted to the metal oxide semiconductor layer of the semiconductor electrode 130 are transmitted to the p-type a-Si layer 226 through the second conductive layer 128, and then, disappear together with the holes.
  • the dye molecules oxidized in the semiconductor electrode 130 as a result of the electron transition are reduced by receiving electrons provided by an oxidation- reduction action of iodine ions ((3I" ⁇ I 3 " + 2e ) in the electrolyte layer 190, and the oxidized iodine ions I 3 - are re -reduced by the electrons arrived at the facing electrode 170, and thus, an operation of the dye-sensitized solar cell 200 is completed.
  • FIG. 3 is a cross-sectional view of a dye-sensitized solar cell 300 according to another embodiment of the present invention.
  • the same reference numerals as in FIGS. 1 and 2 indicate like elements, and thus, the descriptions thereof will not be repeated.
  • the p-n junction diode is included only in the first conductive substrate 110 and not included in the second conductive substrate 150.
  • the tandem structure 220 that includes the p-n junction diode included in the first conductive substrate 110, as depicted in FIG. 2, may be a p-n junction diode formed of amorphous silicon a-Si.
  • the second conductive substrate 150 has a structure including the second transparent substrate 152 and the third conductive layer 154, and the facing electrode 170 is formed on the third conductive layer 154.
  • the third conductive layer 154 may be formed of, for example, FTO.
  • the electrons transmitted to the n-type a-Si layer 222 move to the third conductive layer 154 and the facing electrode 170 along an external circuit (not shown), which is connected from the first conductive substrate 110 to the second conductive substrate 150.
  • the electrons moved to the facing electrode 170 are transmitted to the electrolyte layer 190, which is in an electron deficient state.
  • the electron transmitted to the metal oxide semiconductor layer of the semiconductor electrode 130 are transmitted to the p-type a-Si layer 226 through the second conductive layer 128, and then, disappear together with the holes.
  • the dye molecules oxidized in the semiconductor electrode 130 as a result of the electron transition are reduced by receiving electrons provided by an oxidation- reduction action of iodine ions ((3I" ⁇ I 3 " + 2e ) in the electrolyte layer 190, and the oxidized iodine ions I 3 - are re -reduced by the electrons arrived at the facing electrode 170, and thus, an operation of the dye-sensitized solar cell 300 is completed.
  • FIG. 4 is a cross-sectional view of a dye-sensitized solar cell 400 according to another embodiment of the present invention.
  • the same reference numerals as in FIGS. 1 and 2 indicate like elements, and thus, the descriptions thereof will not be repeated.
  • the p-n junction diode is included only in the second conductive substrate 150 and not included in the first conductive substrate 110.
  • the tandem structure 260 that includes the p-n junction diode included in the second conductive substrate 150, as depicted in FIG. 2, may be a p-n junction diode formed of CIS compound semiconductor.
  • the first conductive substrate 110 has a stack structure including the first transparent substrate 112 and the first conductive layer 114, and the semiconductor electrode 130 is formed on the first conductive layer 114.
  • the first conductive layer 114 may be formed of, for example, FTO.
  • the electron transmitted to the metal oxide semiconductor layer of the semiconductor electrode 130 are transmitted to the third conductive layer 154 formed on the second transparent substrate 152 along an external circuit (not shown) which is connected from the first conductive substrate 110 to the second conductive substrate 150. Afterwards, the electrons disappear together with the holes generated from the p-type CIS compound semiconductor layer 262.
  • the dye molecules oxidized in the semiconductor electrode 130 as a result of the electron transition are reduced by receiving electrons provided by an oxidation- reduction action of iodine ions ((3I " ⁇ I 3 " + 2e ) in the electrolyte layer 190, and the oxidized iodine ions I 3 " are re -reduced by the electrons arrived at the facing electrode 170, and thus, an operation of the dye-sensitized solar cell 400 is completed.
  • a Mo layer, a p-type CIS compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer were sequentially formed on a glass substrate using a metal organic chemical vapor deposition (MOCVD) process.
  • MOCVD metal organic chemical vapor deposition
  • the p-type CIS compound semiconductor layer that absorbs light was formed to a thickness of approximately 2 ⁇ m.
  • an FTO layer having a thickness of approximately 1.5 ⁇ m was formed on the n-type ZnO: Al layer using a spray coating process.
  • a metal oxide semiconductor layer was coated on a conductive glass substrate.
  • the metal oxide semiconductor layer was formed using TiO 2 particles having a diameter of 12 to 20 nm to a thickness of 5 to 15 ⁇ m.
  • Dye molecules formed of Ru complex were chemically adsorbed on a surface of the metal oxide semiconductor layer.
  • Iodine oxidation-reduction liquid electrolyte was used as an electrolyte solution.
  • an electrolyte solution of I 3 /P in which 0.6M of l-hexyl-3-dimethyl-imidazolium iodide, 0.03M of I 2 (iodine), 0.5M of t-butylpyridine, and 0. IM of guanidium thiocyanate are dissolved in a mixed solvent of acetonitrile and valeronitrile was used as the electrolyte.
  • a dye-sensitized solar cell manufactured as described above has a fill factor (FF) of
  • the substrate that does not include the tandem structure that includes a p-n junction diode on a side of the facing electrode that is, when a dye-sensitized solar cell having the same structure as the dye- sensitized solar cell of the manufacturing example except that a Pt electrode was formed on a glass substrate onto which FTO is coated was used, the opening voltage is approximately 0.7V and the energy conversion efficiency is approximately 6%.

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Abstract

Provided is a dye-sensitized solar cell that uses a tandem structure having a p-n junction diode. The dye-sensitized solar cell includes a semiconductor electrode formed on a first conductive substrate, a facing electrode formed on a second conductive substrate, and an electrolyte layer interposed between the semiconductor electrode and the facing electrode. One of the first conductive substrate and the second conductive substrate includes a p-n junction diode.

Description

Description Dye-sensitized solar cells having substrate including p-n junction diode
Technical Field
[1] The present invention relates to a solar cell, and more particularly, to a dye-sensitized solar cell having a substrate including a p-n junction diode.
[2] This work was supported by the Information Technology (IT) Research & Development (R&D) program of the Ministry of Information and Communication (MIC) and the Institute for Information Technology Advancement [2006-S-006-02, Components/Module technology for Ubiquitous Terminals]. Background Art
[3] A dye-sensitized solar cell is a photoelectrochemical solar cell. The main constituent elements of the dye-sensitized solar cell are photosensitive dye molecules that can generate electron-hole pairs by absorbing visible light and a transition metal oxide that transmits the generated electrons. A representative example of a dye-sensitized solar cell is a dye- sensitized solar cell that includes a semiconductor electrode formed of TiO2 nano particles to which dye molecules are adsorbed, a facing electrode coated with Pt or carbon, and an electrolyte solution filled between the semiconductor electrode and the facing electrode. This type of photochemical solar cell has received much attention due to low manufacturing costs per unit power compared to a conventional silicon solar cell.
[4] A dye-sensitized solar cell is operated in the following manner. Dyes excited by sunlight inject electrons into a conduction band of TiO2 nano particles. The injected electrons reach a conductive substrate passing through the TiO2 nano particles, and are transmitted to an external circuit. The electrons that have done an electrical work in the external circuit are injected into the TiO2 nano particles through the facing electrode due to an electron transmission function of the oxidation/reduction electrolyte to reduce the dyes that are deficient in electrons, thereby completing the operation of the dye-sensitized solar cell. Disclosure of Invention Technical Problem
[5] In a conventional dye-sensitized solar cell, a dye adsorbed in a TiO2 layer of a semiconductor electrode generates electrons by absorbing light of a limited wavelength region of the sunlight. Thus, light of other wavelength regions that are not absorbed by the dye or light that is not used for generating electricity even though the light has wavelengths that can be absorbed by the dye are not used for generating electrons. Therefore, the conventional dye-sensitized solar cell has a low energy conversion efficiency, and thus, there is a limit in efficiently using the dye-sensitized solar cell. Technical Solution
[6] To address the above and/or other problems, the present invention provides a dye- sensitized solar cell that can maximize energy conversion efficiency by generating electricity through absorbing a wide range of wavelengths of sunlight.
[7] According to an aspect of the present invention, there is provided a dye-sensitized solar cell comprising: a semiconductor electrode formed on a first conductive substrate; a facing electrode formed on a second conductive substrate; and an electrolyte layer interposed between the semiconductor electrode and the facing electrode, wherein one of the first conductive substrate and the second conductive substrate comprises a p-n junction diode.
[8] One selected from the first conductive substrate and the second conductive substrate may comprise the p-n junction diode and a conductive layer formed on the p-n junction diode. The first conductive substrate may comprise: the p-n junction diode comprising a p-type semiconductor layer and an n-type semiconductor layer; and a first conductive layer formed on the p-n junction diode to contact the p-type semiconductor layer, and the semiconductor electrode may be formed to contact the first conductive layer.
[9] The second conductive substrate may comprise: the p-n junction diode comprising a p-type semiconductor layer and an n-type semiconductor layer; and a second conductive layer formed on the p-n junction diode to contact the n-type semiconductor layer, and the facing electrode may be formed to contact the second conductive layer.
[10] One of the first conductive substrate and the second conductive substrate may comprise: a transparent substrate; a first conductive layer formed on the transparent substrate; the p-n junction diode formed on the first conductive layer; and a second conductive layer formed on the p-n junction diode.
[11] According to another aspect of the present invention, there is provided a dye- sensitized solar cell comprising: a semiconductor electrode formed on a first conductive substrate; a facing electrode formed on a second conductive substrate; and an electrolyte layer interposed between the semiconductor electrode and the facing electrode, wherein the first conductive substrate and the second conductive substrate respectively comprise a p-n junction diode.
[12] The p-n junction diode may have one of a structure in which a p-type CIS compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer are sequentially stacked, and a structure in which a p-type a-Si layer, an i (intrinsic)-type a-Si layer, and an n-type a-Si layer are sequentially stacked.
[13] The first conductive substrate and the second conductive substrate respectively may have p-n junction diode structures different from each other or the same p-n junction diode structure. Advantageous Effects
[14] In a dye-sensitized solar cell according to the present invention, at least one of a first conductive substrate on which a semiconductor electrode is formed and a second conductive substrate on which a facing electrode is formed has a tandem structure that includes a p-n junction diode. The dye-sensitized solar cell according to the present invention has a structure that can generate electricity by absorbing various lights including light that is not absorbed by the dye-sensitized solar cell or light that is not used for generating electricity in a conventional dye-sensitized solar cell. Thus, an opening voltage and the energy conversion efficiency of the dye-sensitized solar cell can be increased. Description of Drawings
[15] The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:
[16] FIG. 1 is a cross-sectional view of a dye-sensitized solar cell according to an embodiment of the present invention;
[17] FIG. 2 is a cross-sectional view of a dye-sensitized solar cell according to another embodiment of the present invention;
[18] FIG. 3 is a cross-sectional view of a dye-sensitized solar cell according to another embodiment of the present invention; and
[19] FIG. 4 is a cross-sectional view of a dye-sensitized solar cell according to another embodiment of the present invention. Best Mode
[20] The present invention will now be described more fully with reference to the accompanying drawings in which exemplary embodiments of the invention are shown.
[21] The invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. It will also be understood that when a layer is referred to as being 'on' another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. In the drawings, the thicknesses of layers and regions are exaggerated for clarity, and thus, the present invention is not limited to the relative size and gap depicted in the reference drawings. Like reference numerals in the drawings denote like elements, and thus their description will not be repeated.
[22] FIG. 1 is a cross-sectional view of a dye-sensitized solar cell 100 according to an em- bodiment of the present invention.
[23] The dye-sensitized solar cell 100 according to an embodiment of the present invention includes a semiconductor electrode 130 formed on a first conductive substrate 110 and a facing electrode 170 formed on a second conductive substrate 150. An electrolyte layer 190 is interposed between the semiconductor electrode 130 and the facing electrode 170.
[24] The first conductive substrate 110 and the second conductive substrate 150 respectively include tandem structures 120 and 160 that respectively include p-n junction diodes.
[25] In the dye-sensitized solar cell 100 of FIG. 1, the first conductive substrate 110 includes a first transparent substrate 112, a first conductive layer 114, the tandem structure 120 including a p-n junction diode, and a second conductive layer 128, which are sequentially stacked. Also, the second conductive substrate 150 includes a second transparent substrate 152, a third conductive layer 154, the tandem structure 160 including a p-n junction diode, and a fourth conductive layer 168, which are sequentially stacked.
[26] The first transparent substrate 112 and the second transparent substrate 152 respectively may be formed of glass or plastic. The first conductive layer 114, the second conductive layer 128, the third conductive layer 154, and the fourth conductive layer 168 respectively may be formed of fluorine-doped tin oxide (FTO), indium tin oxide (ITO), or SnO2. Also, the first transparent substrate 112 and the second transparent substrate 152 respectively may be a conductive transparent substrate formed of a conductive polymer. In this case, it is unnecessary to form the first conductive layer 114 and the third conductive layer 154.
[27] The tandem structures 120 and 160 include p-n junction diodes that respectively include a p-type semiconductor layer and an n-type semiconductor layer.
[28] In the tandem structure 120 that includes the p-n junction diode adjacent to the semiconductor electrode 130, the p-type semiconductor layer may be formed to contact the second conductive layer 128. The semiconductor electrode 130 is formed directly above the second conductive layer 128 so as to be in contact with the second conductive layer 128. That is, in the first conductive substrate 110, the p-type semiconductor layer of the tandem structure 120 that includes the p-n junction diode is disposed to adjacent to the semiconductor electrode 130.
[29] Also, in the tandem structure 160 that includes the p-n junction diode adjacent to the facing electrode 170, the n-type semiconductor layer may be formed to contact the fourth conductive layer 168. The facing electrode 170 is formed directly above the fourth conductive layer 168 so as to be in contact with the fourth conductive layer 168. That is, in the second conductive substrate 150, the n-type semiconductor layer of the tandem structure 160 that includes the p-n junction diode is disposed to adjacent to the facing electrode 170.
[30] The tandem structures 120 and 160 that include a p-n junction diode respectively may be formed in a structure in which a p-type CuInSe2 (CIS) compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer are sequentially stacked. Alternatively, the tandem structures 120 and 160 that include a p-n junction diode may be formed in a structure in which an n-type a-Si layer, an i-type a-Si layer, and a p-type a-Si layer are sequentially stacked. Also, the tandem structures 120 and 160 that include a p-n junction diode may have a p-n junction diode structure comprising an n-type GaAs layer and a p-type GaAs layer.
[31] The first conductive layer 114 and the second conductive layer 128 may be or may not be formed of the same material. For example, the first conductive layer 114 and the second conductive layer 128 may be formed of one material or materials different from each other selected from the group consisting of FTO, ITO, Mo, SnO2, and Ge.
[32] The semiconductor electrode 130 may be a metal oxide layer to which dye molecules are adsorbed. The metal oxide layer may be formed of, for example, TiO2, SnO2, or ZnO to a thickness of 3 to 12μm. Preferably, the metal oxide layer may be formed of TiO2 particles having a size of 15 to 25nm. The dye adsorbed to the metal oxide layer may be a ruthenium complex.
[33] The facing electrode 170 may be formed of Pt.
[34] The electrolyte layer 190 is filled in a space sealed by a sealant 180 between the semiconductor electrode 130 and the facing electrode 170. The electrolyte layer 190 may be formed of an iodine group oxidation-reduction liquid electrolyte. For example, the electrolyte layer 190 may be an I3Vr electrolyte in which 0.6M of l-hexyl-3-dimethyl-imidazolium iodide, 0.03M of I2 (iodine), 0.5M of t-butylpyridine, and 0. IM of guanidium thiocyanate are dissolved in a mixed solvent of acetonitrile and valeronitrile.
[35] The sealant 180 may be formed of a thermoplastic polymer film such as surlyn to a thickness of 30 to 50μm and a width of 1 to 4mm.
[36] FIG. 1 depicts the structures of the first conductive substrate 110 and the second conductive substrate 150, in which the tandem structures 120 and 160 having the p-n junction diode are respectively included. The tandem structures 120 and 160 having the p-n junction diode may have the same structure or may have structures different from each other. Also, one of the tandem structures 120 and 160 having the p-n junction diode may be omitted, if necessary. Mode for Invention
[37] FIG. 2 is a cross-sectional view of a main configuration of a dye-sensitized solar cell
200 according to another embodiment of the present invention. In FIG. 2, the same reference numerals as in FIG. 1 indicate like elements, and thus, the descriptions thereof will not be repeated.
[38] In the dye-sensitized solar cell 200 according to another embodiment of the present invention, a tandem structure 220 includes a p-n junction diode formed of amorphous silicon a-Si, and a tandem structure 260 includes a p-n junction diode formed of a CuInSe2 (CIS) compound semiconductor.
[39] More specifically, the tandem structure 220 that includes the p-n junction diode has a structure in which an n-type a-Si layer 222, an i (intrinsic) type a-Si layer 224, and a p- type a-Si layer 226 are sequentially stacked. The second conductive layer 128 and the semiconductor electrode 130 are sequentially formed on the p-type a-Si layer 226. In the dye-sensitized solar cell 200 of FIG. 2, the first conductive layer 114 and the second conductive layer 128 may be formed of FTO.
[40] The tandem structure 220 that include the p-n junction diode has a structure in which a p-type CIS compound semiconductor layer 262, an n-type CdS layer 264, and an n- type ZnO: Al layer 266 are sequentially stacked. The fourth conductive layer 168 and the facing electrode 170 are sequentially formed on the n-type ZnO:Al layer 266. In the dye-sensitized solar cell 200 of FIG. 2, the third conductive layer 154 may be formed of Mo, and the fourth conductive layer 168 may be formed of FTO.
[41] A method of manufacturing the dye-sensitized solar cell 200 of FIG. 2, according to another embodiment of the present, will now be described. In order to form the first conductive substrate 110, the tandem structure 220 in which the n-type a-Si layer 222, the i (intrinsic)-type a-Si layer 224 and the p-type a-Si layer 226 are sequentially stacked is formed. Afterwards, the transparent second conductive layer 128 is coated on the p-type a-Si layer 226 using FTO or ITO. The semiconductor electrode 130 is formed on the second conductive layer 128. In order to form the semiconductor electrode 130, after forming a metal oxide semiconductor layer using one material selected from, for example, TiO2, SnO2, and ZnO, on the second conductive layer 128, a process of forming a dye molecule layer may be performed by adsorbing the dye molecules on surfaces of metal oxide particles that constitute the metal oxide semiconductor layer.
[42] In order to formed the second conductive substrate 150, the tandem structure 260 is formed, in which the third conductive layer 154, the p-type CIS compound semiconductor layer 262, the n-type CdS layer 264, and the n-type ZnO:Al layer 266 are sequentially stacked on the second transparent substrate 152 . Afterwards, the transparent fourth conductive layer 168 is formed on the an n-type ZnO: Al layer 266 using, for example, FTO or ITO. The facing electrode 170 is formed on the fourth conductive layer 168. The facing electrode 170 may be formed using the following process. If the tandem structure 260 is relatively thermally stable at a high temperature of ap- proximately 4000C, the facing electrode 170 may be formed of Pt on the fourth conductive layer 168 using a high temperature reduction method for a Pt2+ solution. However, if the tandem structure 260 is relatively unstable at a high temperature of approximately 4000C, the facing electrode 170 may be formed of Pt on the fourth conductive layer 168 using a chemical reduction method.
[43] In the dye-sensitized solar cell 200 of FIG. 2, when light enters the dye- sensitized solar cell 200 through the first transparent substrate 112 or the second transparent substrate 152 from the outside, electrons and holes respectively are generated at an n-p interface of the tandem structure 220 that includes the p-n junction diode, at an n-p interface of the tandem structure 260 that includes the p-n junction diode, and at interfaces between the metal oxide particles that constitute the metal oxide semiconductor layer to which dye molecules of the semiconductor electrode 130 are coated. The holes generated from the tandem structure 220 move to the p-type a-Si layer 226, and the electrons move to the n-type a-Si layer 222. The electrons transmitted to the n- type a-Si layer 222 move to holes in the p-type CIS compound semiconductor layer 262 of the second conductive substrate 150 along an external circuit (not shown), which is connected from the first conductive substrate 110 to the second conductive substrate 150. Electrons generated from the p-type CIS compound semiconductor layer 262 due to external light move to the facing electrode 170 through the n-type CdS layer 264 and the n-type ZnO:Al layer 266. The electrons moved to the facing electrode 170 are transmitted to the electrolyte layer 190, which is in an electron deficient state. The electron transmitted to the metal oxide semiconductor layer of the semiconductor electrode 130 are transmitted to the p-type a-Si layer 226 through the second conductive layer 128, and then, disappear together with the holes.
[44] The dye molecules oxidized in the semiconductor electrode 130 as a result of the electron transition are reduced by receiving electrons provided by an oxidation- reduction action of iodine ions ((3I" → I3" + 2e ) in the electrolyte layer 190, and the oxidized iodine ions I3- are re -reduced by the electrons arrived at the facing electrode 170, and thus, an operation of the dye-sensitized solar cell 200 is completed.
[45] FIG. 3 is a cross-sectional view of a dye-sensitized solar cell 300 according to another embodiment of the present invention. In FIG. 3, the same reference numerals as in FIGS. 1 and 2 indicate like elements, and thus, the descriptions thereof will not be repeated.
[46] In the dye-sensitized solar cell 300 of FIG. 3, the p-n junction diode is included only in the first conductive substrate 110 and not included in the second conductive substrate 150.
[47] In FIG. 3, the tandem structure 220 that includes the p-n junction diode included in the first conductive substrate 110, as depicted in FIG. 2, may be a p-n junction diode formed of amorphous silicon a-Si.
[48] The second conductive substrate 150 has a structure including the second transparent substrate 152 and the third conductive layer 154, and the facing electrode 170 is formed on the third conductive layer 154. The third conductive layer 154 may be formed of, for example, FTO.
[49] In the dye-sensitized solar cell 300 of FIG. 3, when light enters the dye- sensitized solar cell 300 through the first transparent substrate 112 and the second transparent substrate 152 from the outside, electrons and holes respectively are generated at an n-p interface of the tandem structure 220 that includes the p-n junction diode, and at interfaces between the metal oxide particles in the metal oxide semiconductor layer to which dye molecules of the semiconductor electrode 130 are coated. The generated holes move to the p-type a-Si layer 226, and the electrons move to the n-type a-Si layer 222. The electrons transmitted to the n-type a-Si layer 222 move to the third conductive layer 154 and the facing electrode 170 along an external circuit (not shown), which is connected from the first conductive substrate 110 to the second conductive substrate 150. The electrons moved to the facing electrode 170 are transmitted to the electrolyte layer 190, which is in an electron deficient state. The electron transmitted to the metal oxide semiconductor layer of the semiconductor electrode 130 are transmitted to the p-type a-Si layer 226 through the second conductive layer 128, and then, disappear together with the holes.
[50] The dye molecules oxidized in the semiconductor electrode 130 as a result of the electron transition are reduced by receiving electrons provided by an oxidation- reduction action of iodine ions ((3I" → I3" + 2e ) in the electrolyte layer 190, and the oxidized iodine ions I3- are re -reduced by the electrons arrived at the facing electrode 170, and thus, an operation of the dye-sensitized solar cell 300 is completed.
[51] FIG. 4 is a cross-sectional view of a dye-sensitized solar cell 400 according to another embodiment of the present invention. In FIG. 4, the same reference numerals as in FIGS. 1 and 2 indicate like elements, and thus, the descriptions thereof will not be repeated.
[52] In the dye-sensitized solar cell 400 of FIG. 4, the p-n junction diode is included only in the second conductive substrate 150 and not included in the first conductive substrate 110.
[53] In FIG. 4, the tandem structure 260 that includes the p-n junction diode included in the second conductive substrate 150, as depicted in FIG. 2, may be a p-n junction diode formed of CIS compound semiconductor.
[54] The first conductive substrate 110 has a stack structure including the first transparent substrate 112 and the first conductive layer 114, and the semiconductor electrode 130 is formed on the first conductive layer 114. The first conductive layer 114 may be formed of, for example, FTO.
[55] In the dye-sensitized solar cell 400 of FIG. 4, when light enters the dye- sensitized solar cell 400 through the first transparent substrate 112 and the second transparent substrate 152 from the outside, electrons and holes respectively are generated at an n-p interface of the tandem structure 260 that includes the p-n junction diode and at interfaces between the metal oxide particles in the metal oxide semiconductor layer to which dye molecules of the semiconductor electrode 130 are coated. Electrons generated from the n-type CdS layer 264 and the n-type ZnO:Al layer 266 move to the facing electrode 170 through the fourth conductive layer 168. The electrons moved to the facing electrode 170 are transmitted to the electrolyte layer 190, which is in an electron deficient state. Also, the electron transmitted to the metal oxide semiconductor layer of the semiconductor electrode 130 are transmitted to the third conductive layer 154 formed on the second transparent substrate 152 along an external circuit (not shown) which is connected from the first conductive substrate 110 to the second conductive substrate 150. Afterwards, the electrons disappear together with the holes generated from the p-type CIS compound semiconductor layer 262.
[56] The dye molecules oxidized in the semiconductor electrode 130 as a result of the electron transition are reduced by receiving electrons provided by an oxidation- reduction action of iodine ions ((3I" → I3 " + 2e ) in the electrolyte layer 190, and the oxidized iodine ions I3 " are re -reduced by the electrons arrived at the facing electrode 170, and thus, an operation of the dye-sensitized solar cell 400 is completed.
[57] Manufacturing Example
[58] An exemplary method of manufacturing a dye-sensitized solar cell that includes a substrate having a tandem structure that includes a p-n junction diode on a side of a facing electrode similar to the structure of FIG. 4 will now be described.
[59] A Mo layer, a p-type CIS compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer were sequentially formed on a glass substrate using a metal organic chemical vapor deposition (MOCVD) process. In particular, the p-type CIS compound semiconductor layer that absorbs light was formed to a thickness of approximately 2 μm. Afterwards, an FTO layer having a thickness of approximately 1.5 μm was formed on the n-type ZnO: Al layer using a spray coating process. After spraying an H2PtCl6-XH2O (hydrogen hexachloroplatinate (IV) hydrate: Aldrich, 99.9%) 2-propanol solution on the FTO layer, a facing electrode was formed by annealing the resultant product at a temperature of 4000C for 30 minutes.
[60] In order to form a semiconductor electrode, a metal oxide semiconductor layer was coated on a conductive glass substrate. The metal oxide semiconductor layer was formed using TiO2 particles having a diameter of 12 to 20 nm to a thickness of 5 to 15 μm. Dye molecules formed of Ru complex were chemically adsorbed on a surface of the metal oxide semiconductor layer. Iodine oxidation-reduction liquid electrolyte was used as an electrolyte solution. In the present embodiment, an electrolyte solution of I3 /P in which 0.6M of l-hexyl-3-dimethyl-imidazolium iodide, 0.03M of I2 (iodine), 0.5M of t-butylpyridine, and 0. IM of guanidium thiocyanate are dissolved in a mixed solvent of acetonitrile and valeronitrile was used as the electrolyte.
[61] A dye-sensitized solar cell manufactured as described above has a fill factor (FF) of
65%, an open voltage of 1.13V, a short circuit current of 13 mA/m2, and an energy conversion efficiency of 9.5%.
[62] As a comparative example, in the case that the substrate that does not include the tandem structure that includes a p-n junction diode on a side of the facing electrode is used, that is, when a dye-sensitized solar cell having the same structure as the dye- sensitized solar cell of the manufacturing example except that a Pt electrode was formed on a glass substrate onto which FTO is coated was used, the opening voltage is approximately 0.7V and the energy conversion efficiency is approximately 6%.

Claims

Claims
[1] A dye-sensitized solar cell comprising: a semiconductor electrode formed on a first conductive substrate; a facing electrode formed on a second conductive substrate; and an electrolyte layer interposed between the semiconductor electrode and the facing electrode, wherein one of the first conductive substrate and the second conductive substrate comprises a p-n junction diode.
[2] The dye-sensitized solar cell of claim 1, wherein one selected from the first conductive substrate and the second conductive substrate comprises the p-n junction diode and a conductive layer formed on the p-n junction diode.
[3] The dye-sensitized solar cell of claim 2, wherein the p-n junction diode has a structure in which a p-type CIS compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer are sequentially stacked.
[4] The dye-sensitized solar cell of claim 2, wherein the p-n junction diode has a structure in which a p-type a-Si layer, an i (intrinsic) -type a-Si layer, and an n- type a-Si layer are sequentially stacked.
[5] The dye-sensitized solar cell of claim 2, wherein the conductive layer is formed of fluorine-doped tin oxide (FTO) or indium tin oxide (ITO).
[6] The dye-sensitized solar cell of claim 1, wherein the first conductive substrate comprises: the p-n junction diode comprising a p-type semiconductor layer and an n-type semiconductor layer; and a first conductive layer formed on the p-n junction diode to contact the p-type semiconductor layer, and the semiconductor electrode is formed to contact the first conductive layer.
[7] The dye-sensitized solar cell of claim 1, wherein the second conductive substrate comprises: the p-n junction diode comprising a p-type semiconductor layer and an n-type semiconductor layer; and a second conductive layer formed on the p-n junction diode to contact the n-type semiconductor layer, and the facing electrode is formed to contact the second conductive layer.
[8] The dye-sensitized solar cell of claim 1, wherein one of the first conductive substrate and the second conductive substrate comprises: a transparent substrate; a first conductive layer formed on the transparent substrate; the p-n junction diode formed on the first conductive layer; and a second conductive layer formed on the p-n junction diode.
[9] The dye-sensitized solar cell of claim 8, wherein the first conductive layer and the second conductive layer respectively formed of FTO and ITO.
[10] The dye-sensitized solar cell of claim 8, wherein the first conductive layer is formed of Mo and the second conductive layer is formed of FTO or ITO.
[11] A dye-sensitized solar cell comprising: a semiconductor electrode formed on a first conductive substrate; a facing electrode formed on a second conductive substrate; and an electrolyte layer interposed between the semiconductor electrode and the facing electrode, wherein the first conductive substrate and the second conductive substrate respectively comprise a p-n junction diode.
[12] The dye-sensitized solar cell of claim 11, wherein the p-n junction diode has one of a structure in which a p-type CIS compound semiconductor layer, an n-type CdS layer, and an n-type ZnO:Al layer are sequentially stacked, and a structure in which a p-type a-Si layer, an i (intrinsic)-type a-Si layer, and an n-type a-Si layer are sequentially stacked.
[13] The dye-sensitized solar cell of claim 12, wherein the first conductive substrate and the second conductive substrate respectively have p-n junction diode structures different from each other.
[14] The dye-sensitized solar cell of claim 12, wherein the first conductive substrate and the second conductive substrate have the same p-n junction diode structure.
PCT/KR2008/003687 2007-11-21 2008-06-26 Dye-sensitized solar cells having substrate including p-n junction diode WO2009066848A1 (en)

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