WO2009099282A2 - Solar cell having multiple transparent conductive layers and manufacturing method thereof - Google Patents

Solar cell having multiple transparent conductive layers and manufacturing method thereof Download PDF

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Publication number
WO2009099282A2
WO2009099282A2 PCT/KR2009/000506 KR2009000506W WO2009099282A2 WO 2009099282 A2 WO2009099282 A2 WO 2009099282A2 KR 2009000506 W KR2009000506 W KR 2009000506W WO 2009099282 A2 WO2009099282 A2 WO 2009099282A2
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Prior art keywords
layer
transparent conductive
conductive layer
solar cell
oxygen
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PCT/KR2009/000506
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French (fr)
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WO2009099282A3 (en
Inventor
Kwang-Sun Ji
Youngjoo Eo
Heon Min Lee
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Lg Electronics Inc.
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Priority to CN2009801040342A priority Critical patent/CN101933159B/en
Priority to JP2010545806A priority patent/JP2011511470A/en
Priority to EP09708789.4A priority patent/EP2238627A4/en
Publication of WO2009099282A2 publication Critical patent/WO2009099282A2/en
Publication of WO2009099282A3 publication Critical patent/WO2009099282A3/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to a solar cell having multiple transparent conductive layers and a manufacturing method thereof. More specifically, the present invention relates to a solar cell that increases a rate of sunlight absorbed into a photoelectric conversion layer by forming a transparent conductive layer into a plurality of layers having different oxygen contents and different light absorbing coefficients and a manufacturing method thereof.
  • An object of the present invention is to provide a solar cell that can increase efficiency by increasing transmittance of sunlight by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different oxygen contents and different light absorbing coefficients and a manufacturing method thereof.
  • Another object of the present invention is to provide a solar cell that can increase efficiency by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different refractive indexes so that incident sunlight is absorbed again into a photoelectric conversion layer even when the incident sunlight passes through the photoelectric conversion layer, is reflected from a rear electrode, and again reaches the transparent conductive layer and a manufacturing method thereof.
  • Still another object of the present invention is to provide a solar cell that includes a transparent conductive layer having excellent crystallinity and large crystal grain size on the whole by configuring the transparent conductive layer of the solar cell in a structure that includes a first layer having high oxygen content and a second layer deposited on the first layer so that the excellent crystallinity and large crystal grain size of a first layer can be maintained even in the second layer and a manufacturing method thereof.
  • the present invention provides a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion layer, the transparent conductive layer comprising: a first layer having a first light absorbing coefficient; and a second layer that is formed on the first layer and has a second light absorbing coefficient higher than the first light absorbing coefficient.
  • Each transparent conductive layer may be configured of one layer or a plurality of layers.
  • the oxygen content of the first layer may be relatively higher than the oxygen content of the second layer.
  • the oxygen contents of the first and second layers may be reduced as the first and second layers become further away from the substrate.
  • crystallinity of the first layer may be relatively higher than that of the second layer.
  • the crystallinity of the first and second layers of the transparent conductive layer of the present invention may be defined by a concept that includes a crystallized degree of a material forming the layers, that is, a volume ratio occupied by a crystal grain size per a unit volume and a concept that includes a crystal grain size of these layers.
  • the refractive indexes of the first and second layers may be different from each other.
  • the optical bandgap energy of the first layer may be relatively lower than that of the second layer.
  • the specific resistance of the first layer may be relatively higher than that of the second layer.
  • the transparent conductive layer may include any one selected from a group consisting of zinc oxide (ZnO) based material, tin oxide (SnO 2 ), and indium tin oxide (ITO) (In 2 O 3 : SnO 2 ) or may be doped with at least one selected from a group consisting of aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), and lithium (Li).
  • ZnO zinc oxide
  • SnO 2 tin oxide
  • ITO indium tin oxide
  • the solar cell of the present invention may be configured to include, as an intermediate layer, a layer having intermediate properties of the above-mentioned properties between the transparent conductive layers configured of the first and second layers of the above-mentioned multiple layers.
  • the first layer of the transparent conductive layer of the present invention may be called a transmitting layer since it has relatively excellent light transmittance and the second layer of the transparent conductive layer may be called a conductive layer since it may have light transmittance smaller than the first layer but has significantly reduced specific resistance and may be used as a conductive layer that may move carriers generated from the photoelectric conversion layer due to low contact resistance with the photoelectric conversion layer deposited later.
  • the present invention provides a solar cell including a substrate, a transparent conductive layer, a photoelectric conversion layer, wherein the transparent conductive layer has a higher light absorbing coefficient at a surface adjacent to the photoelectric conversion layer than that at a surface to which light is incident.
  • oxygen concentration at the surface to which light is incident may be higher than oxygen concentration at the surface adjacent to the photoelectric conversion layer.
  • the transparent conductive layer may reduce the oxygen concentration at the same layer.
  • the present invention provides a manufacturing method of a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion, the manufacturing method comprising: depositing the transparent conductive layer having reduced oxygen content on the substrate as it becomes further away from the substrate.
  • the transparent conductive layer may be deposited while gradually reducing the volume fraction of oxygen among gases introduced at the time of deposition.
  • the present invention provides a manufacturing method of a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion, the manufacturing method comprising: depositing a first layer on the substrate under a gas atmosphere including oxygen to prepare the transparent conductive layer; and depositing a second layer on the first layer under a gas atmosphere including oxygen having lower concentration than that of oxygen used in the first layer deposition step.
  • the transparent conductive layer may include any one selected from a group consisting of zinc oxide (ZnO)-based material, tin oxide (SnO 2 ), and indium tin oxide (ITO) (In 2 O 3 : SnO 2 ) or may be doped with at least one selected from a group consisting of aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), and lithium (Li).
  • ZnO zinc oxide
  • SnO 2 tin oxide
  • ITO indium tin oxide
  • the efficiency of the solar cell can be increased by increasing transmittance of sunlight by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different oxygen contents and different light absorbing coefficients.
  • the efficiency of the solar cell can be increased by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different refractive indexes so that incident sunlight is absorbed again into a photoelectric conversion layer even when the incident sunlight passes through the photoelectric conversion layer, is reflected from a rear electrode, and again reaches the transparent conductive layer.
  • the solar cell that includes a transparent conductive layer having the excellent crystallinity and large crystal grain size on the whole by configuring the transparent conductive layer of the solar cell in a structure that includes a first layer having high oxygen content and a second layer deposited on the first layer so that the excellent crystallinity and large crystal grain size of a first layer can be maintained even in the second layer.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of a transparent conductive layer according to one embodiment of the present invention
  • FIG. 2 is a graph showing an amount of oxygen contained in each layer included in the transparent conductive layer of FIG. 1;
  • FIGS. 3 and 4 are graphs showing transmittance of the transparent conductive layer whose surface is textured according to one embodiment of the present invention
  • FIG. 5 a graph showing a haze ratio of the transparent conductive layer according to one embodiment of the present invention
  • FIG. 6 is a diagram showing optical properties of a solar cell to which the transparent conductive layer according to one embodiment of the present invention is applied;
  • FIGS. 7 and 8 are graphs showing electrical properties of the transparent conductive layer according to one embodiment of the present invention.
  • FIG. 9 is an image showing surface shapes of the transparent conductive layer according to one embodiment of the present invention.
  • FIG. 10 is a graph showing an improved crystallinity of the transparent conductive layer when oxygen is added at the time of depositing the transparent conductive layer according to one embodiment of the present invention.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of a transparent conductive layer according to one embodiment of the present invention.
  • a transparent conductive layer 100 applied to a solar cell of the present invention includes a transmitting layer 130, an intermediate layer 150, and a conductive layer 170 that are sequentially deposited on a glass substrate 110.
  • the transmitting layer 130, the intermediate layer 150, and the conductive layer 170 are divided according to an amount of oxygen contained in each layer. That is, each layer consists of the same materials, while the amount of the oxygen of the layers is different from each other.
  • the transmitting layer 130 is a layer containing a largest amount of oxygen
  • the conductive layer 170 is a layer containing a smallest amount of oxygen
  • the intermediate layer 150 which is a layer deposited while the amount of oxygen is reduced after the deposition of the transmitting layer 130, is a boundary layer between the transmitting layer 130 and the conductive layer 170.
  • composition materials of the transmitting layer 130, the intermediate layer 150, and the conductive layer 170 zinc oxide (ZnO)-based materials can be basically used but tin oxide (SnO 2 ) and indium tin oxide (ITO) (In 2 O 3 : SnO 2 ), etc., can be used, wherein the basic material can be doped with aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), lithium (Li), and the like.
  • the zinc oxide having high haze ratio is a value defined by (diffusion transmittance) / (straight transmittance) 100%.
  • the haze ratio is represented by the following equation 1.
  • T D represents diffusion transmittance
  • T S represents straight transmittance
  • T T represents total transmittance
  • the high haze ratio means that most of incident sunlight can be absorbed into a photoelectric conversion layer by allowing light diffused or transmitted among sunlight incident through the glass substrate 110 to occupy high ratio.
  • the transmitting layer 130 is a layer containing a relatively large amount of oxygen.
  • the light transmittance can be relatively higher by the property of a large content of oxygen. Therefore, the transmitting layer 130 can perform a role of reducing loss of sunlight incident through the glass substrate 110.
  • the transmitting layer 130 contains a large amount of oxygen, crystallinity is excellent and a crystal grain size also increases.
  • the conductive layer 170 which includes a layer containing a much smaller amount of oxygen than the transmitting layer 130, is a layer deposited while the amount of oxygen is reduced in the deposition process. According to this property, as the conductive layer 170 has a relatively higher light absorbing coefficient than the transmitting layer 130, the optical bandgap energy Eg becomes higher.
  • the transmitting layer 130 serves as a seeding layer and the property of the transmitting layer 130 having high oxygen content advantageously serves to grow the conductive layer 170.
  • the conductive layer 170 has low oxygen content, light transmittance can be relatively low, but specific resistance is significantly reduced. Due to the low specific resistance, the contact resistance with the photoelectric conversion layer deposited later is low, such that carriers generated by light absorption in the photoelectric conversion layer can be moved in the conductive layer 170.
  • the intermediate layer 150 which is a layer deposited while the amount of oxygen is reduced in the sequential deposition processes of the transmitting layer 130 and the conductive layer 170, serves to maintain the crystallinity of the transmitting layer 130 up to the conductive layer 170.
  • Table 1 indicates a difference between absorption coefficients of each of the transmitting layer 130 and the conductive layer 170 about main absorption wavelength bands of the solar cell.
  • FIGS. 3 and 4 are graphs showing the transmittance of the surface-textured transparent conductive layer 100.
  • the transparent layer 100 of the present invention improves total transmittance T T in the wavelength band of 400 nm to 1200 nm as compared to the related art.
  • FIG. 5 is a graph showing a haze ratio of the transparent conductive layer 100 of the present invention.
  • the transparent conductive layer 100 of the present invention has the haze ratio of about 60% in the wavelength region of about 550 nm and has the haze ratio of 40 % or more in average, such that it is suitable for applying to the transparent conductive layer.
  • R represents reflectance
  • n s represents refractive index of the skin
  • n c represents refractive index of the coating.
  • This optical property simulation is performed under the assumption that light having the wavelength of about 550 nm in a superstrate solar cell is vertically incident.
  • the refractive indexes of each material used for the optical property simulation are shown in Table 2 and the optical properties of the solar cell to which the transparent conductive layer 100 of the present invention simulated by using equation 2 and data shown in table 2 is applied is shown in FIG. 7.
  • FIG. 6 is a diagram showing optical properties in the case where light incident through the glass substrate 110 passes through the photoelectric conversion layer, is reflected from a rear electrode made of metal or metal oxide, and is returned back to the glass substrate 110.
  • the solar cell using the transparent conductive layer 100 of the present invention reflects light incident through the glass substrate 110 from the rear electrode such that it is returned back, about 14 % of light is reflected back to the photoelectric conversion layer, such that the efficiency of the solar cell can be improved by the re-absorption of light.
  • FIGS. 7 and 8 are graphs showing electrical properties of the transparent conductive layer 100 according to the present invention.
  • the transparent conductive layer 100 shows a value of 10 ⁇ or less that is a generally required surface resistance (Rs) value of the transparent conductive layer and a value of 5 ⁇ 10 -4 or less that is a generally required specific resistance value of the transparent conductive layer, such that it can be applied to the solar cell.
  • Rs surface resistance
  • the optical band gap energy Eg is slightly lowered by the addition of oxygen, but shows a value of 3.0 eV that is a generally required Eg value, such that these properties can be also applied to the solar cell.
  • FIG. 9 is an image showing surface shapes of the transparent conductive layer 100 according to one embodiment of the present invention. As shown in FIG. 9, when comparing with the transparent conductive layer in the related art, it can be appreciated that the transparent conductive layer is uniform by significantly reducing a crater having an irregularly small size.
  • materials to be used as the transparent conductive layer are deposited on the glass substrate 110.
  • the materials can use zinc oxide (ZnO)-based materials as the basic materials.
  • the deposition can be performed by a sputtering, a chemical vapor deposition, etc., which are known deposition methods.
  • the above materials deposited on the glass substrate 110 under atmosphere having a high initial oxygen ratio can function as the transmitting layer 130
  • the conductive layer 170 can be formed.
  • the transmitting layer 130 can serve as the seed layer 170.
  • FIG. 10 is a graph showing the crystallinity improvement of the transparent conductive layer when oxygen is added at the time of deposition.
  • the higher the volume fraction occupied by oxygen among gases introduced at the time of deposition the more the crystallinity increases, such that the transmitting layer 130 deposited under the atmosphere showing the high oxygen ratio shows the excellent crystallinity properties.
  • This transmitting layer 130 advantageously serves to grow the conductive layer 170, such that the properties, such as the excellent crystallinity and the large crystal grain, etc., are transferred up to the conductive layer 170.
  • the transmitting layer 130 and the conductive layer 170 can be sequentially formed by naturally lowering the oxygen fraction by continuously performing the deposition under the oxygen atmosphere as described above.
  • the transmitting layer 130 can be deposited under the atmosphere having a high oxygen fraction and then, the conductive layer 170 can be deposited under the atmosphere having a low oxygen fraction.
  • the structure of the solar cell including the transparent conductive layer there may be a solar cell (not shown) wherein a glass substrate, a transparent conductive layer of the present invention as a lower transparent conductive layer, an amorphous silicon solar cell layer (a-si : H p/i/n layers) as a photoelectric conversion layer, a transparent conductive layer of the present invention as a lower transparent conductive layer, and a rear electrode are sequentially formed.
  • the solar cell including the transparent conductive layer of the present invention can be manufactured the methods well known to those skilled in the art and therefore, the detailed description of the manufacturing method will not be repeated.
  • the amorphous silicon type solar cell using the transparent electrode of the present invention is described, but the transparent electrode can be applied to the solar cell having the photoelectric conversion layer by changing factors such as compounds, dye sensitivity, organic materials, etc.

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Abstract

The present invention provides a solar cell that increases a rate of sunlight absorbed into a photoelectric conversion layer by forming a transparent conductive layer into a plurality of layers having different oxygen contents and different light absorbing coefficients and a manufacturing method thereof. The solar cell of the present invention includes a substrate, a transparent conductive layer, and a photoelectric conversion layer, wherein the transparent conductive layer comprises a first layer having a first light absorbing coefficient; and a second layer that is formed on the first layer and has a second light absorbing coefficient higher than the first light absorbing coefficient.

Description

SOLAR CELL HAVING MULTIPLE TRANSPARENT CONDUCTIVE LAYERS AND MANUFACTURING METHOD THEREOF
The present invention relates to a solar cell having multiple transparent conductive layers and a manufacturing method thereof. More specifically, the present invention relates to a solar cell that increases a rate of sunlight absorbed into a photoelectric conversion layer by forming a transparent conductive layer into a plurality of layers having different oxygen contents and different light absorbing coefficients and a manufacturing method thereof.
Recently, due to problems such as a rapid rise in oil prices, an environmental problem of the earth, exhaustion of fossil energy, waste treatment in nuclear power generation, position selection according to construction of a new power plant, etc., interest in renewable energy has increased and among others, research and development for a solar cell, which is a pollution-free energy source, has actively been progressed.
The solar cell, which is a device converting light energy into electrical energy using a photovoltaic effect, has recently been receiving much attention according to an increased demand of alternative energy.
In the solar cell, it is important to increase conversion efficiency that is associated with a rate of converting incident sunlight into electric energy. Various researches to increase the conversion efficiency have been progressed and research to increase a rate of sunlight absorbed into the solar cell by reducing light loss as much as possible so as to increase the efficiency of the solar cell has been progressed.
An object of the present invention is to provide a solar cell that can increase efficiency by increasing transmittance of sunlight by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different oxygen contents and different light absorbing coefficients and a manufacturing method thereof.
Another object of the present invention is to provide a solar cell that can increase efficiency by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different refractive indexes so that incident sunlight is absorbed again into a photoelectric conversion layer even when the incident sunlight passes through the photoelectric conversion layer, is reflected from a rear electrode, and again reaches the transparent conductive layer and a manufacturing method thereof.
Still another object of the present invention is to provide a solar cell that includes a transparent conductive layer having excellent crystallinity and large crystal grain size on the whole by configuring the transparent conductive layer of the solar cell in a structure that includes a first layer having high oxygen content and a second layer deposited on the first layer so that the excellent crystallinity and large crystal grain size of a first layer can be maintained even in the second layer and a manufacturing method thereof.
To achieve the above objects, the present invention provides a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion layer, the transparent conductive layer comprising: a first layer having a first light absorbing coefficient; and a second layer that is formed on the first layer and has a second light absorbing coefficient higher than the first light absorbing coefficient. Each transparent conductive layer may be configured of one layer or a plurality of layers.
In the present invention, the oxygen content of the first layer may be relatively higher than the oxygen content of the second layer.
In the present invention, the oxygen contents of the first and second layers may be reduced as the first and second layers become further away from the substrate.
In the present invention, crystallinity of the first layer may be relatively higher than that of the second layer. The crystallinity of the first and second layers of the transparent conductive layer of the present invention may be defined by a concept that includes a crystallized degree of a material forming the layers, that is, a volume ratio occupied by a crystal grain size per a unit volume and a concept that includes a crystal grain size of these layers.
In the present invention, the refractive indexes of the first and second layers may be different from each other.
In the present invention, the optical bandgap energy of the first layer may be relatively lower than that of the second layer.
In the present invention, the specific resistance of the first layer may be relatively higher than that of the second layer.
In the present invention, the transparent conductive layer may include any one selected from a group consisting of zinc oxide (ZnO) based material, tin oxide (SnO2), and indium tin oxide (ITO) (In2O3 : SnO2) or may be doped with at least one selected from a group consisting of aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), and lithium (Li).
The solar cell of the present invention may be configured to include, as an intermediate layer, a layer having intermediate properties of the above-mentioned properties between the transparent conductive layers configured of the first and second layers of the above-mentioned multiple layers.
The first layer of the transparent conductive layer of the present invention may be called a transmitting layer since it has relatively excellent light transmittance and the second layer of the transparent conductive layer may be called a conductive layer since it may have light transmittance smaller than the first layer but has significantly reduced specific resistance and may be used as a conductive layer that may move carriers generated from the photoelectric conversion layer due to low contact resistance with the photoelectric conversion layer deposited later.
To achieve the above object, the present invention provides a solar cell including a substrate, a transparent conductive layer, a photoelectric conversion layer, wherein the transparent conductive layer has a higher light absorbing coefficient at a surface adjacent to the photoelectric conversion layer than that at a surface to which light is incident.
In the present invention, oxygen concentration at the surface to which light is incident may be higher than oxygen concentration at the surface adjacent to the photoelectric conversion layer.
In the present invention, the transparent conductive layer may reduce the oxygen concentration at the same layer.
To achieve the above objects, the present invention provides a manufacturing method of a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion, the manufacturing method comprising: depositing the transparent conductive layer having reduced oxygen content on the substrate as it becomes further away from the substrate.
In the manufacturing method of the present invention, the transparent conductive layer may be deposited while gradually reducing the volume fraction of oxygen among gases introduced at the time of deposition.
To achieve the above objects, the present invention provides a manufacturing method of a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion, the manufacturing method comprising: depositing a first layer on the substrate under a gas atmosphere including oxygen to prepare the transparent conductive layer; and depositing a second layer on the first layer under a gas atmosphere including oxygen having lower concentration than that of oxygen used in the first layer deposition step.
In the manufacturing method of the present invention, the transparent conductive layer may include any one selected from a group consisting of zinc oxide (ZnO)-based material, tin oxide (SnO2), and indium tin oxide (ITO) (In2O3 : SnO2) or may be doped with at least one selected from a group consisting of aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), and lithium (Li).
According to the present invention, the efficiency of the solar cell can be increased by increasing transmittance of sunlight by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different oxygen contents and different light absorbing coefficients.
Further, the efficiency of the solar cell can be increased by forming a transparent conductive layer of the solar cell in a multi-layer structure including a plurality of layers having different refractive indexes so that incident sunlight is absorbed again into a photoelectric conversion layer even when the incident sunlight passes through the photoelectric conversion layer, is reflected from a rear electrode, and again reaches the transparent conductive layer.
Also, the solar cell that includes a transparent conductive layer having the excellent crystallinity and large crystal grain size on the whole by configuring the transparent conductive layer of the solar cell in a structure that includes a first layer having high oxygen content and a second layer deposited on the first layer so that the excellent crystallinity and large crystal grain size of a first layer can be maintained even in the second layer.
The above and other objects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which:
FIG. 1 is a cross-sectional view schematically showing a configuration of a transparent conductive layer according to one embodiment of the present invention;
FIG. 2 is a graph showing an amount of oxygen contained in each layer included in the transparent conductive layer of FIG. 1;
FIGS. 3 and 4 are graphs showing transmittance of the transparent conductive layer whose surface is textured according to one embodiment of the present invention;
FIG. 5 a graph showing a haze ratio of the transparent conductive layer according to one embodiment of the present invention;
FIG. 6 is a diagram showing optical properties of a solar cell to which the transparent conductive layer according to one embodiment of the present invention is applied;
FIGS. 7 and 8 are graphs showing electrical properties of the transparent conductive layer according to one embodiment of the present invention;
FIG. 9 is an image showing surface shapes of the transparent conductive layer according to one embodiment of the present invention; and
FIG. 10 is a graph showing an improved crystallinity of the transparent conductive layer when oxygen is added at the time of depositing the transparent conductive layer according to one embodiment of the present invention.
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view schematically showing a configuration of a transparent conductive layer according to one embodiment of the present invention.
As shown in FIG. 1, a transparent conductive layer 100 applied to a solar cell of the present invention includes a transmitting layer 130, an intermediate layer 150, and a conductive layer 170 that are sequentially deposited on a glass substrate 110.
The transmitting layer 130, the intermediate layer 150, and the conductive layer 170 are divided according to an amount of oxygen contained in each layer. That is, each layer consists of the same materials, while the amount of the oxygen of the layers is different from each other. Referring to FIG. 2 that shows oxygen contents of each layer, the transmitting layer 130 is a layer containing a largest amount of oxygen, the conductive layer 170 is a layer containing a smallest amount of oxygen, and the intermediate layer 150, which is a layer deposited while the amount of oxygen is reduced after the deposition of the transmitting layer 130, is a boundary layer between the transmitting layer 130 and the conductive layer 170.
Meanwhile, as composition materials of the transmitting layer 130, the intermediate layer 150, and the conductive layer 170, zinc oxide (ZnO)-based materials can be basically used but tin oxide (SnO2) and indium tin oxide (ITO) (In2O3 : SnO2), etc., can be used, wherein the basic material can be doped with aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), lithium (Li), and the like. Among others, it is preferable to use the zinc oxide having high haze ratio. Herein, the haze ratio is a value defined by (diffusion transmittance) / (straight transmittance) 100%. The haze ratio is represented by the following equation 1.
Figure PCTKR2009000506-appb-I000001
Wherein, TD represents diffusion transmittance, TS represents straight transmittance, and TT represents total transmittance.
The high haze ratio means that most of incident sunlight can be absorbed into a photoelectric conversion layer by allowing light diffused or transmitted among sunlight incident through the glass substrate 110 to occupy high ratio.
As described above, the transmitting layer 130 is a layer containing a relatively large amount of oxygen. The light transmittance can be relatively higher by the property of a large content of oxygen. Therefore, the transmitting layer 130 can perform a role of reducing loss of sunlight incident through the glass substrate 110. On the other hand, since the transmitting layer 130 contains a large amount of oxygen, crystallinity is excellent and a crystal grain size also increases.
The conductive layer 170, which includes a layer containing a much smaller amount of oxygen than the transmitting layer 130, is a layer deposited while the amount of oxygen is reduced in the deposition process. According to this property, as the conductive layer 170 has a relatively higher light absorbing coefficient than the transmitting layer 130, the optical bandgap energy Eg becomes higher.
Meanwhile, when the conductive layer 170 is deposited, the transmitting layer 130 serves as a seeding layer and the property of the transmitting layer 130 having high oxygen content advantageously serves to grow the conductive layer 170.
Since the conductive layer 170 has low oxygen content, light transmittance can be relatively low, but specific resistance is significantly reduced. Due to the low specific resistance, the contact resistance with the photoelectric conversion layer deposited later is low, such that carriers generated by light absorption in the photoelectric conversion layer can be moved in the conductive layer 170.
On the other hand, the intermediate layer 150, which is a layer deposited while the amount of oxygen is reduced in the sequential deposition processes of the transmitting layer 130 and the conductive layer 170, serves to maintain the crystallinity of the transmitting layer 130 up to the conductive layer 170.
Table 1 indicates a difference between absorption coefficients of each of the transmitting layer 130 and the conductive layer 170 about main absorption wavelength bands of the solar cell.
Table 1
Figure PCTKR2009000506-appb-T000001
It can be appreciated from Table 1 that there is a difference in absorption coefficients of about 9% in average in a wavelength band of 400 nm to 1000 nm. Therefore, in the case of the present invention using a film having a relatively small absorption coefficient as the transmitting layer 130, it can contribute to improving the efficiency of the solar cell.
Meanwhile, FIGS. 3 and 4 are graphs showing the transmittance of the surface-textured transparent conductive layer 100.
As shown in FIGS. 3 and 4, it can be appreciated that the transparent layer 100 of the present invention improves total transmittance TT in the wavelength band of 400 nm to 1200 nm as compared to the related art.
Meanwhile, FIG. 5 is a graph showing a haze ratio of the transparent conductive layer 100 of the present invention.
As shown in FIG. 5, the transparent conductive layer 100 of the present invention has the haze ratio of about 60% in the wavelength region of about 550 nm and has the haze ratio of 40 % or more in average, such that it is suitable for applying to the transparent conductive layer.
The improved effect of the efficiency of the solar cell provided with the transparent conductive layer 100 according to the present invention can be apparently appreciated from the optical property simulation results using the following equation 2.
Figure PCTKR2009000506-appb-I000002
Wherein, R represents reflectance, ns represents refractive index of the skin, and nc represents refractive index of the coating.
This optical property simulation is performed under the assumption that light having the wavelength of about 550 nm in a superstrate solar cell is vertically incident. The refractive indexes of each material used for the optical property simulation are shown in Table 2 and the optical properties of the solar cell to which the transparent conductive layer 100 of the present invention simulated by using equation 2 and data shown in table 2 is applied is shown in FIG. 7.
Table 2
Figure PCTKR2009000506-appb-T000002
FIG. 6 is a diagram showing optical properties in the case where light incident through the glass substrate 110 passes through the photoelectric conversion layer, is reflected from a rear electrode made of metal or metal oxide, and is returned back to the glass substrate 110.
As shown in FIG. 6, in the solar cell using the transparent conductive layer in the related art, when the incident light passes through the photoelectric conversion layer, is reflected from the rear electrode, and is returned back, 85 % of the incident light reaches the glass substrate, but in the case of the solar cell using the transparent conductive layer of the present invention, since each of the conductive layer 170 and the transmitting layer 130 has different refractive indexes, light is reflected back to the photoelectric layer so that only about 71% of light reaches the glass substrate.
In other words, when the solar cell using the transparent conductive layer 100 of the present invention reflects light incident through the glass substrate 110 from the rear electrode such that it is returned back, about 14 % of light is reflected back to the photoelectric conversion layer, such that the efficiency of the solar cell can be improved by the re-absorption of light.
Meanwhile, FIGS. 7 and 8 are graphs showing electrical properties of the transparent conductive layer 100 according to the present invention.
As shown in FIG. 7, the transparent conductive layer 100 shows a value of 10 Ω or less that is a generally required surface resistance (Rs) value of the transparent conductive layer and a value of 5 ×10-4 or less that is a generally required specific resistance value of the transparent conductive layer, such that it can be applied to the solar cell.
Further, as shown in FIG. 8, the optical band gap energy Eg is slightly lowered by the addition of oxygen, but shows a value of 3.0 eV that is a generally required Eg value, such that these properties can be also applied to the solar cell.
Meanwhile, FIG. 9 is an image showing surface shapes of the transparent conductive layer 100 according to one embodiment of the present invention. As shown in FIG. 9, when comparing with the transparent conductive layer in the related art, it can be appreciated that the transparent conductive layer is uniform by significantly reducing a crater having an irregularly small size.
Further, when performing an etching on the transparent conductive layer 100 in order to form the surface texturing structure, when comparing with the etching on the transparent conductive layer in the related art, it can be observed that the damage of the transparent conductive layer is small and a fine crease is formed on the surface. This shows that as described above, the high oxygen content, the excellent crystallinity, and the large crystal grain size, which are maintained in the transmitting layer 130, are also maintained in the conductive layer 170.
Hereinafter, a manufacturing method of the transparent conductive layer 100 according to the present invention will be described.
First, under the oxygen atmosphere, materials to be used as the transparent conductive layer are deposited on the glass substrate 110. As described above, the materials can use zinc oxide (ZnO)-based materials as the basic materials. The deposition can be performed by a sputtering, a chemical vapor deposition, etc., which are known deposition methods. The above materials deposited on the glass substrate 110 under atmosphere having a high initial oxygen ratio can function as the transmitting layer 130
Thereafter, if the materials for the transparent conductive layer are continuously deposited on the glass substrate 110, the amount of peripheral oxygen is reduced, such that the layer having a small oxygen content is deposited on the top. By these processes, the conductive layer 170 can be formed. When depositing the conductive layer, the transmitting layer 130 can serve as the seed layer 170.
FIG. 10 is a graph showing the crystallinity improvement of the transparent conductive layer when oxygen is added at the time of deposition. Referring to FIG. 10, the higher the volume fraction occupied by oxygen among gases introduced at the time of deposition, the more the crystallinity increases, such that the transmitting layer 130 deposited under the atmosphere showing the high oxygen ratio shows the excellent crystallinity properties. This transmitting layer 130 advantageously serves to grow the conductive layer 170, such that the properties, such as the excellent crystallinity and the large crystal grain, etc., are transferred up to the conductive layer 170.
Meanwhile, the transmitting layer 130 and the conductive layer 170 can be sequentially formed by naturally lowering the oxygen fraction by continuously performing the deposition under the oxygen atmosphere as described above. However, the transmitting layer 130 can be deposited under the atmosphere having a high oxygen fraction and then, the conductive layer 170 can be deposited under the atmosphere having a low oxygen fraction.
As one embodiment of the structure of the solar cell including the transparent conductive layer according to the present invention, there may be a solar cell (not shown) wherein a glass substrate, a transparent conductive layer of the present invention as a lower transparent conductive layer, an amorphous silicon solar cell layer (a-si : H p/i/n layers) as a photoelectric conversion layer, a transparent conductive layer of the present invention as a lower transparent conductive layer, and a rear electrode are sequentially formed. The solar cell including the transparent conductive layer of the present invention can be manufactured the methods well known to those skilled in the art and therefore, the detailed description of the manufacturing method will not be repeated.
The amorphous silicon type solar cell using the transparent electrode of the present invention is described, but the transparent electrode can be applied to the solar cell having the photoelectric conversion layer by changing factors such as compounds, dye sensitivity, organic materials, etc.
Although the present invention has been described in detail with reference to its presently preferred embodiment, it will be understood by those skilled in the art that various modifications and equivalents can be made without departing from the spirit and scope of the present invention, as set forth in the appended claims. Also, the substances of each constituent explained in the specification can be easily selected and processed by those skilled in the art from the well-known various substances. Also, those skilled in the art can remove a part of the constituents as described in the specification without deterioration of performance or can add constituents for improving the performance. Furthermore, those skilled in the art can change the order to methodic steps explained in the specification according to environments of processes or equipments. Thus, it is intended that the present invention covers the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (15)

  1. A solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion layer, the transparent conductive layer comprising:
    a first layer having a first light absorbing coefficient; and
    a second layer that is formed on the first layer and has a second light absorbing coefficient higher than the first light absorbing coefficient.
  2. The solar cell according to claim 1, wherein the oxygen content of the first layer is relatively higher than the oxygen content of the second layer.
  3. The solar cell according to claim 1, wherein the oxygen contents of the first and second layers are reduced as the first and second layers become further away from the substrate.
  4. The solar cell according to claim 1, wherein the crystallinity of the first layer is relatively higher than that of the second layer.
  5. The solar cell according to claim 1, wherein the refractive indexes of the first and second layers are different from each other.
  6. The solar cell according to claim 1, wherein the optical bandgap energy of the first layer is relatively lower than that of the second layer.
  7. The solar cell according to claim 1, wherein the specific resistance of the first layer is relatively higher than that of the second layer.
  8. The solar cell according to claim 1, wherein the transparent conductive layer includes any one selected from a group consisting of zinc oxide (ZnO)-based material, tin oxide (SnO2), and indium tin oxide (ITO) (In2O3 : SnO2) or is doped with at least one selected from a group consisting of aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), and lithium (Li).
  9. A solar cell including a substrate, a transparent conductive layer, a photoelectric conversion layer,
    wherein the transparent conductive layer has a higher light absorbing coefficient at a surface adjacent to the photoelectric conversion layer than that at a surface to which light is incident.
  10. The solar cell according to claim 9, wherein oxygen concentration at the surface to which light is incident is higher than oxygen concentration at the surface adjacent to the photoelectric conversion layer.
  11. The solar cell according to claim 9, wherein the transparent conductive layer reduces the oxygen concentration at the same layer.
  12. A manufacturing method of a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion, the manufacturing method comprising:
    depositing the transparent conductive layer having reduced oxygen content on the substrate as it becomes further away from the substrate.
  13. The manufacturing method according to claim 12, wherein the transparent conductive layer is deposited while gradually reducing the volume fraction of oxygen among gases introduced at the time of deposition.
  14. A manufacturing method of a solar cell including a substrate, a transparent conductive layer, and a photoelectric conversion, the manufacturing method comprising:
    depositing a first layer on the substrate under a gas atmosphere including oxygen to prepare the transparent conductive layer; and
    depositing a second layer on the first layer under a gas atmosphere including oxygen having lower concentration than that of oxygen used in the first layer deposition step.
  15. The manufacturing method according to any one of claims 12 to 14, wherein the transparent conductive layer includes any one selected from a group consisting of zinc oxide (ZnO)-based material, tin oxide (SnO2), and indium tin oxide (ITO) (In2O3 : SnO2) or is doped with at least one selected from a group consisting of aluminum (Al), gallium (Ga), fluorine (F), germanium (Ge), magnesium (Mg), boron (B), indium (In), tin (Sn), and lithium (Li).
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