KR20110044442A - Transparent electrode for a thin film solar cell and fabricating method thereof - Google Patents
Transparent electrode for a thin film solar cell and fabricating method thereof Download PDFInfo
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- KR20110044442A KR20110044442A KR1020090101111A KR20090101111A KR20110044442A KR 20110044442 A KR20110044442 A KR 20110044442A KR 1020090101111 A KR1020090101111 A KR 1020090101111A KR 20090101111 A KR20090101111 A KR 20090101111A KR 20110044442 A KR20110044442 A KR 20110044442A
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- 239000010409 thin film Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 25
- 239000000758 substrate Substances 0.000 claims abstract description 69
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- 239000002238 carbon nanotube film Substances 0.000 claims abstract description 30
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
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- 229910004613 CdTe Inorganic materials 0.000 description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
The present invention relates to a transparent electrode for a solar cell and a method of manufacturing the same, and more particularly to a transparent electrode for a solar cell and improved manufacturing method of the adhesion between the electrode material and the glass substrate in the conventional transparent electrode for thin film solar cells.
Recently, interest in renewable energy is increasing due to high oil prices and environmental problems. Unlike other energy sources, solar cells, which are photovoltaic devices that convert sunlight into electrical energy, are endless and environmentally friendly, and their importance is increasing over time.
Solar cells can be classified into crystalline silicon solar cells using wafers used in semiconductors and thin film solar cells using deposition techniques on substrates such as glass. Currently, crystalline silicon solar cells have a high market share, but despite the stability of technology and high conversion efficiency, it is difficult to secure economic feasibility. Therefore, the market share of thin film solar cells is expected to increase with high efficiency and low price.
The thin film solar cell is a representative next-generation cell that uses a low-cost substrate such as glass and manufactures a thin-film solar cell using a light absorption layer material such as silicon on a low-cost substrate, unlike a conventional form using the entire crystalline silicon as a solar absorption substrate. .
Such thin film solar cells can be roughly divided into amorphous silicon thin film solar cells (a-Si solar cells), compound thin film solar cells using CdTe or CIS, dye-sensitized thin film solar cells, and organic thin film solar cells according to the material of the light absorption layer. In recent years, multilayer thin film solar cells have also been used to improve the efficiency of amorphous silicon thin film solar cells. Multilayer thin film solar cell is a multilayer of amorphous silicon and microcrystalline silicon and used as light absorbing layer. It can be divided into tandem type and triple type, and tandem thin film solar cell is formed on amorphous silicon. It is a structure in which a microcrystalline silicon film is stacked, and a triple type thin film solar cell is a laminate of two layers of microcrystalline silicon films on amorphous silicon, and has an advantage of reducing initial degradation due to amorphous silicon.
However, these thin film solar cells are still lower in conversion efficiency than conventional crystalline silicon solar cells, and various studies have been continued to achieve high efficiency with a small area, and development of thin film solar cells having a more stable structure is required. It is becoming.
One problem to be solved by the present invention is to provide a transparent electrode for a solar cell having a stable structure by improving the adhesion between the transparent substrate and the transparent conductive film.
Another object of the present invention is to provide a method for manufacturing the transparent electrode for solar cells.
Another object of the present invention is to provide a thin film solar cell comprising the transparent electrode for the solar cell.
One aspect of the present invention for achieving the above object is a transparent substrate; A carbon nanotube (CNT) film formed on the transparent substrate; And it relates to a transparent electrode for a solar cell comprising a transparent conductive film formed on the carbon nanotube conductive film.
Another aspect of the present invention for achieving the above object is to prepare a transparent substrate; Forming a carbon nanotube film on the transparent substrate; And it relates to a method for manufacturing a transparent electrode for a solar cell comprising the step of forming a transparent conductive film on the carbon nanotube film.
The method may further comprise the step of cleaning the transparent substrate, wherein the step of cleaning the transparent substrate is at least 10 minutes for each step using distilled water (DI water), isopropyl alcohol (IPA), or a strong base solution. It is good to perform more than this. The carbon nanotube film may be formed by chemical vapor deposition (TEM), thermal chemical vapor deposition (TCVD), microwave plasma enhanced chemical vapor deposition (MPECVD), or the like.
The forming of the carbon nanotube film may include: i) depositing a metal catalyst on the substrate; ii) etching the metal catalyst deposited on the substrate to form nano-sized metal catalyst particles; iii) placing the substrate in a deaired chamber and heating it; And iv) growing a carbon nanotube by supplying a reactant to the chamber.
Another aspect of the present invention for achieving the above object relates to a thin film solar cell comprising a transparent electrode, a light absorption layer and a counter electrode for a solar cell according to embodiments of the present invention.
According to the embodiments of the present invention, an ohmic contact between the transparent substrate and the transparent conductive layer by inserting a carbon nanotube (CNT) film as an intermediate layer between the transparent substrate and the transparent conductive layer in the transparent electrode for a thin film solar cell. It is possible to improve the adhesion between the two layers, and even if the transparent conductive film is damaged by the post-processing texturing, etc. CNT film can take the role of a transparent electrode can provide a transparent electrode of a more stable structure. .
Hereinafter, with reference to the accompanying drawings will be described in more detail with respect to the present invention.
In order to more clearly describe the present invention, parts irrelevant to the description are omitted, and the accompanying drawings are outlined for clarity of understanding of the present invention and are enlarged in order to clearly express various layers and regions in the drawings. However, the scope of the present invention is not limited by the thickness, size, ratio, etc. shown in the drawings.
In the present specification, the transparent electrode for a solar cell basically means including a transparent substrate and a transparent conductive film.
1 is a schematic cross-sectional view of a transparent electrode according to an embodiment of the present invention. Referring to Figure 1, one aspect according to an embodiment of the present invention is a
In the conventional transparent electrode for a thin film solar cell, a transparent conductive film is directly formed on a substrate, but the present inventors have found that a problem may occur in the adhesion between the transparent conductive film and the substrate. In order to enable ohmic contact between the conductive layers and to improve adhesion between the two layers, a carbon nanotube (CNT) film was inserted into the inter-layer.
A thin film solar cell is manufactured by forming a thin film on a substrate. The thin film solar cell basically transmits electrons and holes produced from a thin film made of a light absorbing material that absorbs light to generate electrons and holes, and thin films of upper and lower portions thereof. It consists of electrodes. The upper electrode generally includes a transparent conductive oxide film (TCO-Transparent Conductive Oxide) because it must pass through the light to the light absorbing layer. According to the main material of the light absorption layer, it can be divided into amorphous silicon thin film solar cell (a-Si solar cell), compound thin film solar cell using CdTe or CIS, dye-sensitized thin film solar cell, organic thin film solar cell, and embodiments of the present invention. The transparent electrode for solar cells can be used for all of the above-mentioned thin film solar cells, and besides, it can be used for stacked solar cells such as tandem thin film solar cells or triple thin film solar cells as next generation solar cells.
example Transparent substrates that can be used for the transparent electrode for solar cells according to embodiments of the present invention include, but are not limited to, a glass substrate and a polymer film substrate, and more preferably nothing is coated glass substrate. When a polymer film substrate is applied, a glass substrate is more preferable because it is difficult to form a zinc oxide film by a high temperature chemical vapor deposition method.
example The transparent conductive film usable for the transparent electrode for a solar cell according to the embodiments of the present invention may be zinc oxide (ZnO), indium oxide (ITO), tin oxide (SnO 2 : F: fluorinated doped tin oxide), or fluorine doping. Tin oxide (FTO), ZnO: B, ZnO: Al, SnO 2 , ZnO-Ga, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 , or SnO 2 -Sb 2 O 3 , but It is not necessarily limited thereto, and most preferably zinc oxide. This is because the indium, which is a main material for ITO membranes, is expensive and the electrical properties and surface properties are not excellent, and in the case of tin oxide layer, the membrane may be damaged during the hydrogen plasma treatment.
The transparent electrode for a solar cell according to the embodiments of the present invention includes a CNT film as an intermediate layer between the transparent substrate and the transparent conductive film to facilitate crystal growth of a transparent conductive film such as a zinc oxide film. It is possible to increase the conductivity and improve the adhesion between the two layers. The thickness of the CNT film is preferably 5 to 200 nm, more preferably 10 to 100 nm. If it is out of the above range, there may be a problem that the conductivity inside the film is increased to decrease the conductivity.
It is preferable that the thickness of the said transparent conductive film is 200-2000 nm, More preferably, it is 300-1500 nm. If it is out of the above range, there may be a problem that the transmittance is reduced to reduce the short-circuit current.
The transparent conductive layer may further include a dopant to improve conductivity, and the dopant may be gallium (Ga), aluminum oxide (Al 2 O 3 ), boron (B), fluorine (F), or indium (In). It may be one or more selected from the group consisting of, but is not limited thereto.
Another aspect of the present invention for achieving the above object is to prepare a transparent substrate; Forming a carbon nanotube film on the transparent substrate; And it relates to a method for manufacturing a transparent electrode for a solar cell comprising the step of forming a transparent conductive film on the carbon nanotube film.
The method may further comprise a step of cleaning to remove impurities remaining on the surface of the substrate to increase adhesion to other layers as a pretreatment, wherein the step of cleaning the transparent substrate is distilled water (DI water), isopropyl It is recommended to perform at least 10 minutes for each step using alcohol (IPA) or strong base solution. The carbon nanotube film may be formed by Chemical Vapor Deposition (CVD), Thermal Chemical Vapor Deposition (TCVD), Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD), or the like. .
Specifically, the forming of the carbon nanotube film may include: i) depositing a metal catalyst on the substrate; ii) etching the metal catalyst deposited on the substrate to form nano-sized metal catalyst particles; iii) placing the substrate in a deaired chamber and heating it; And iv) growing a carbon nanotube by supplying a reactant to the chamber. This is to use the carbon nanotubes are grown on the nano-sized metal catalyst particles, the CNT film formation method by the chemical vapor deposition method is advantageous for large area, it is advantageous for the continuous process.
As the metal catalyst, iron (Fe), nickel (Ni), cobalt (Co), Ni-MgO, or Fe-Mo-MgO may be deposited on the substrate by thermal deposition or sputtering, and the metal deposited on the substrate. The catalyst is etched using ammonia, hydrogen gas and the like to form nano-sized fine metal catalyst particles, and then the substrate is placed in an air-free chamber and heated to 600 ° C. to 800 ° C., followed by carbon-containing reactor. The carbon nanotubes are grown on the nanosized metal catalyst particles by flowing into the chamber. The reaction temperature must be higher than the melting point of the metal catalyst. If the reaction temperature is not higher than the catalyst temperature, the catalyst is not activated when the energy state of the metal catalyst is lower than Ea (activation energy), thereby reducing the yield of the reaction. Or because the reaction rarely occurs.
C 2 H 2 , CH 4 , C 2 H 4 , C 2 H 6 , or CO may be used as the reactor, and the carbon nanotube film may have a thickness of 5 to 200 nm, more preferably. It is preferable to form it in 10-100 nm.
The method of forming the transparent conductive film on the CNT film may be formed by a sputtering process or a vacuum deposition method, the thickness of the transparent conductive film is preferably formed to 200 to 2000nm, more preferably 300 to 1500nm Good to do.
Another aspect of the present invention for achieving the above object relates to a thin film solar cell comprising a transparent electrode for a solar cell according to embodiments of the present invention.
Hereinafter, an amorphous silicon thin film solar cell will be described as an example.
2 is a schematic cross-sectional view of a thin film solar cell including a transparent electrode according to an embodiment of the present invention. Referring to FIG. 2, the thin film
The
The light absorbing layer 200 is formed on the
The semiconductor layer generates holes and electrons by sunlight and the generated holes and electrons are collected in the P layer and the N layer, respectively. In order to enhance the efficiency of collecting holes and electrons, the P layer is used. A PIN structure is more preferable than the PN structure which consists only of and N layers. When the pin structure is formed, the I layer is depleted by the P layer and the N layer to generate an electric field therein, and the holes and electrons generated by sunlight are drift by the electric field, respectively. Collected in P and N layers.
The
The thin film solar cell configured as described above operates as follows. When light is incident on the solar cell from the outside, electrons and holes are generated by the light energy incident from the light absorption layer 200, and the electrons are diffused into the N-type silicon layer and the holes are respectively diffused into the P-type silicon layer. When polarization of the charge carrier occurs, a potential difference occurs at both sides of the semiconductor. At this time, when the N-type silicon layer and the P-type silicon layer are connected, electric power is generated by the movement of the electrons and holes.
Hereinafter, the present invention will be described in more detail with reference to the following examples in order to help understand the present invention, but various modifications may be made to the embodiments according to the present invention, and the scope of the present invention is limited to the following examples. It should not be interpreted.
Example 1
After cutting 0.7mm thick flat glass to 200x200mm, the substrate was placed in an air-free chamber, infused with argon (Ar) gas, heated to 650 ° C, and reacted with acetylene containing carbon (C). 2 H 2 ) 70 nm of carbon nanotubes having an average diameter of about 30 nm were grown on the nano-sized metal catalyst particles by flowing a gas into the chamber. Subsequently, aluminum oxide-doped zinc oxide (AZO: ZnO: Al) was deposited on the formed carbon nanotube layer by about 1 μm, and a PIN layer, which is a light absorption region, was deposited by chemical vapor deposition.
P layer is deposited to 7 nm thickness by PECVD using silane, methane, diborane and hydrogen gas on the glass on which the transparent electrode is deposited, and a buffer layer using silane, methane and hydrogen gas to improve adhesion with I layer. Was deposited to a thickness of 6 nm. I layer was deposited to 200-300 nm thickness using silane gas. N-type silicon layers having a thickness of 25 to 35 nm were formed using silane, hydrogen, and phosphine gas. The PECVD apparatus used consists of multi-chambers to prevent contamination due to interlayer doping.
After deposition of the light absorbing layer, a zinc oxide (ZnO) layer was formed to a thickness of 80 nm with a counter electrode by sputtering, and a silver (Ag) layer was deposited to a thickness of 210 nm to manufacture a solar cell.
Comparative Example 1
A thin film solar cell was manufactured in the same manner as in Example 1 except that a vu-type product of Asahi Glass Co., Ltd. was used as a glass substrate, and a ZnO film was immediately formed on the upper portion thereof. In the vu-type product of Asahi Glass, a SiO x layer and a TiO x layer exist between the transparent conductive film composed of a tin oxide (SnO 2 : F) layer and the transparent glass substrate.
Experimental Example 1-Adhesiveness Measurement
The adhesion between the transparent substrate and the transparent conductive film of the solar cells manufactured in Example 1 and Comparative Example 1 was determined as FF (fill factor), which is one of the efficiency measurement factors, and is shown in Table 1 below.
The adhesion between the transparent substrate and the transparent conductive film can be judged to be better as the fill factor (FF) increases. Referring to the results of the above experimental example, in the case of Example 1 including a carbon nanotube film between the substrate and the transparent conductive film, the adhesion between the transparent substrate and the transparent conductive film than Comparative Example 1 in which a commercially available glass substrate is generally used We can confirm that sex is good.
Although the present invention has been described in detail with reference to preferred embodiments of the present invention, these are merely exemplary, and those skilled in the art to which the present invention pertains have various modifications and equivalents therefrom. It will be appreciated that embodiments are possible. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.
1 is a schematic cross-sectional view of a transparent electrode according to an embodiment of the present invention,
2 is a schematic cross-sectional view of a thin film solar cell including a transparent electrode according to an embodiment of the present invention.
* Description of the symbols for the main parts of the drawings *
10: transparent electrode 100: substrate
110: carbon nanotube film 120: transparent conductive film
200: light absorption layer 300: counter electrode
Claims (16)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020090101111A KR20110044442A (en) | 2009-10-23 | 2009-10-23 | Transparent electrode for a thin film solar cell and fabricating method thereof |
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| KR1020090101111A KR20110044442A (en) | 2009-10-23 | 2009-10-23 | Transparent electrode for a thin film solar cell and fabricating method thereof |
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| KR20110044442A true KR20110044442A (en) | 2011-04-29 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219401A (en) * | 2013-04-12 | 2013-07-24 | 陕西师范大学 | Method of improving current density and cell efficiency of solar cell and cell structure |
| CN103700779A (en) * | 2012-09-28 | 2014-04-02 | 北京富纳特创新科技有限公司 | Organic light emitting diode |
| CN103943697A (en) * | 2014-03-28 | 2014-07-23 | 京东方科技集团股份有限公司 | Flexible and transparent solar cell and preparation method thereof |
-
2009
- 2009-10-23 KR KR1020090101111A patent/KR20110044442A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700779A (en) * | 2012-09-28 | 2014-04-02 | 北京富纳特创新科技有限公司 | Organic light emitting diode |
| CN103219401A (en) * | 2013-04-12 | 2013-07-24 | 陕西师范大学 | Method of improving current density and cell efficiency of solar cell and cell structure |
| CN103943697A (en) * | 2014-03-28 | 2014-07-23 | 京东方科技集团股份有限公司 | Flexible and transparent solar cell and preparation method thereof |
| US9711664B2 (en) | 2014-03-28 | 2017-07-18 | Boe Technology Group Co., Ltd. | Flexible transparent solar cell and production process of the same |
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