KR101582419B1 - Method of fabricating electron collector for solar cell and electron collector for flexible solar cell - Google Patents
Method of fabricating electron collector for solar cell and electron collector for flexible solar cell Download PDFInfo
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- KR101582419B1 KR101582419B1 KR1020140098348A KR20140098348A KR101582419B1 KR 101582419 B1 KR101582419 B1 KR 101582419B1 KR 1020140098348 A KR1020140098348 A KR 1020140098348A KR 20140098348 A KR20140098348 A KR 20140098348A KR 101582419 B1 KR101582419 B1 KR 101582419B1
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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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- 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
Abstract
Description
The present invention relates to a method for manufacturing an electron collecting layer for a solar cell and an electron collecting layer for a flexible solar cell produced thereby.
Research on renewable and clean alternative energy sources such as solar energy, wind power, and hydro power is actively being conducted to solve the global environmental problems caused by depletion of fossil energy and its use.
Among these, there is a great interest in solar cells that change electric energy directly from sunlight. Here, a solar cell refers to a cell that generates a current-voltage by utilizing a photovoltaic effect that absorbs light energy from sunlight to generate electrons and holes.
Currently, np diode-type silicon (Si) single crystal based solar cells with a light energy conversion efficiency of more than 20% can be manufactured and used for actual solar power generation. Compound semiconductors such as gallium arsenide (GaAs) There is also solar cell using. However, since inorganic semiconductor-based solar cells require highly refined materials for high efficiency, a large amount of energy is consumed in the purification of raw materials, and expensive processes are required in the process of making single crystals or thin films using raw materials And the manufacturing cost of the solar cell can not be lowered, which has been a hindrance to a large-scale utilization.
Accordingly, in order to manufacture a solar cell at a low cost, it is necessary to drastically reduce the cost of the material or manufacturing process used as a core of the solar cell. As an alternative to the inorganic semiconductor-based solar cell, Type solar cells and organic solar cells have been actively studied.
In recent years, silicon-based, organic dye-based, and new perovskite-based solar cells are in the process of developing solar cells. Currently, perovskite-based solar cells are emerging as the most promising solar technologies. The highest efficiency of the perovskite solar cell reported to date is 15%, which is expected to be further improved.
Since perovskite has a special crystal structure such as calcium titanium dioxide, perovskite solar cells are attractive, and this structure enables high charge transport mobility and long diffusion distance in solar cells, This allows long distance travel without loss, and as a result, electrons and holes can pass through a thicker light absorbing layer and absorb relatively more light.
(AM is a monovalent organic ammonium ion or Cs +, M is a divalent metal ion, and X is a halogen ion) used as a light absorbing and activating material of a perovskite-based solar cell is highly absorbent Based on the coefficient characteristics, it is highly possible to develop ultra-low-cost low-cost solar cells. However, since the metal oxide thin film-based electron collecting layer which is necessary for extracting electrons into the electrode provides excellent electron mobility and low recombination characteristics by removing defects and securing crystallinity, it is necessary to perform a high temperature heat treatment process ), Which makes it impossible to fabricate a flexible substrate necessary for producing a flexible solar cell.
A high-temperature heat treatment process (180 to 500 ° C) is required. Therefore, when a high temperature heat treatment is performed to fabricate a flexible solar cell, it is impossible to easily form the electron collecting layer by heat treatment at a high temperature on a flexible substrate.
The present invention provides a method of manufacturing a low temperature process electron collecting layer having a high electron mobility which can not be secured at a low temperature by a conventional metal oxide electron collecting layer. Thus, a perovskite-based And to provide a high-efficiency flexible solar cell.
That is, the present invention aims to provide an electron collecting layer which omits a heat treatment at a high temperature and which solves the problems of defects in the electron collecting layer sufficiently even through a low-temperature process, thereby maintaining high efficiency.
A method of manufacturing an electron collecting layer for a solar cell according to an embodiment of the present invention includes the steps of disposing a flexible substrate in a process chamber; Preparing an electron collector precursor; Injecting the electron collector precursor into the process chamber using an inert gas; And forming an electron collector thin film layer on the flexible substrate using a low temperature vacuum process.
The low-temperature vacuum process is preferably an ALD (Atomic Layer Deposition), a PEALD (Plasma Enhanced Atomic Layer Deposition) process, or a sputter process. The low-temperature vacuum process is preferably carried out at a temperature of 50 ° C to 150 ° C. When the low-temperature vacuum process is a PEALD process, O 2 is injected after the electron collector precursor is injected, and the plasma process is performed.
The electron collector precursor is preferably an amorphous metal oxide precursor.
Meanwhile, the method of manufacturing an electron collecting layer for a solar cell according to a further embodiment of the present invention may further include a step of pre-purging or post-purging the process chamber using an inert gas .
According to the method of the present invention, an electron collecting layer having an excellent electron mobility characteristic comparable to that of a conventional metal oxide electron collecting layer is formed in a low-temperature process, thereby securing high electron collection characteristics on a flexible substrate. In addition, the photoelectrons generated due to the fast electron collection characteristics can be quickly collected to secure a high short-circuit current, thereby realizing a high-efficiency solar cell.
1 shows a flowchart of a method for manufacturing an electron collecting layer for a solar cell according to an embodiment of the present invention.
FIG. 2 is a view for explaining an improvement in characteristics of a metal oxide electron collecting layer based on a low temperature process having excellent electron transfer characteristics according to an embodiment of the present invention.
FIG. 3 shows XPS analysis results in the case where the electron collecting layer is formed according to the conventional method and the case where the electron collecting layer is formed according to the method of the present invention.
FIG. 4 shows a current density-voltage graph of a low-temperature process-based perovskite thin film solar cell using three kinds of electron collecting layers.
Fig. 5 shows the result of measuring the PL lifetime for three kinds of electron collecting layers.
6 shows the impedance spectroscopy measurement result.
FIG. 7 shows a flowchart of a method of manufacturing a solar cell according to an embodiment of the present invention.
Various embodiments are now described with reference to the drawings, wherein like reference numerals are used throughout the drawings to refer to like elements. For purposes of explanation, various descriptions are set forth herein to provide an understanding of the present invention. It is evident, however, that such embodiments may be practiced without these specific details. In other instances, well-known structures and devices are shown in block diagram form in order to facilitate describing the embodiments.
The following description provides a simplified description of one or more embodiments in order to provide a basic understanding of embodiments of the invention. This section is not a comprehensive overview of all possible embodiments and is not intended to identify key elements or to cover the scope of all embodiments of all elements. Its sole purpose is to present the concept of one or more embodiments in a simplified form as a prelude to the more detailed description that is presented later.
The present invention provides a low temperature process electron collecting layer method having a high electron mobility which can not be secured at a low temperature by a conventional metal oxide electron collecting layer, Thereby providing a flexible solar cell.
According to the method for manufacturing an electron collecting layer according to an embodiment of the present invention, an electron collecting layer is provided that omits a heat treatment at a high temperature and solves problems of defects in the electron collecting layer sufficiently even through a low temperature process, thereby maintaining high efficiency .
1 shows a flowchart of a method for manufacturing an electron collecting layer for a solar cell according to an embodiment of the present invention.
Referring to FIG. 1, a method for manufacturing an electron collecting layer for a solar cell according to an embodiment of the present invention includes the steps of: (S110) placing a flexible substrate in a process chamber; Preparing an electron collector precursor (S 120); Injecting an electron collector precursor into the process chamber using an inert gas (S 130); And a step (S 140) of forming an electron collector thin film layer on the flexible substrate using a low temperature vacuum process.
In step S 110, a flexible substrate is placed in the process chamber. The flexible substrate can be any flexible substrate, and there is no particular limitation thereto. The process chamber is a chamber for performing the electron collection layer forming process, and is a chamber through which vacuum can be maintained through the vacuum equipment.
In step S 120, an electron collector precursor is prepared. As the electron collector precursor, an amorphous metal oxide precursor is used. As an example thereof, TTIP (Titanium (IV) isopropoxide) may be used as a Ti precursor, which is merely an example, but is not limited thereto.
In step S 130, an inert gas is used to inject the electron collector precursor into the process chamber. The inert gas used is Ar, He or the like, and is not particularly limited thereto.
The inert gas acts as a carrier gas for injecting the electron collector precursor into the process chamber and is also used as a gas to clean the chamber as a purging gas.
In step S 140, an electron collector thin film layer is formed on the flexible substrate using a low-temperature vacuum process.
The low-temperature vacuum process may be one of ALD (Atomic Layer Deposition), PEALD (Plasma Enhanced Atomic Layer Deposition), or a sputtering process. In the method for manufacturing an electron-collecting layer according to the present invention, it is preferable to use the above three methods. On the other hand, in the case of the sol-gel method, which is a conventional high-temperature process technology, a large number of organic substances may exist on the surface, which may act as defects, resulting in a problem of inefficiency. However, using the above method has an advantage that there is no problem arising from the presence of such organic matter. That is, when the low temperature vacuum process according to an embodiment of the present invention is used, the control of the interface is advantageous.
As used herein, the term "low temperature" means a temperature lower than a temperature of 180 DEG C to 500 DEG C, which is the temperature at which the comparison object was used to fabricate the conventional metal oxide thin film-based electron collecting layer. Preferably from 50 [deg.] C to 150 [deg.] C.
In this case, when PEALD is used in a low-temperature vacuum process, O 2 is injected after the electron collector precursor is injected, and a plasma treatment is further performed.
On the other hand, the process chamber may further include pre-purging or post-purging using an inert gas. In the case of pre-purge, the interior of the chamber is cleaned before injecting the amorphous metal oxide source into the process chamber, and the post-purge is to clean the chamber interior after the process in the process chamber.
Hereinafter, the contents of the present invention will be further described with reference to specific embodiments and drawings.
First, Titanium (IV) isopropoxide was prepared as a Ti precursor to prepare an electron collecting layer according to an embodiment of the present invention. High purity Ar was prepared as carrier gas and purging gas of Ti precursor.
After the pre-purging in the ALD process chamber for 10 seconds, the Ti precursor source was injected into the chamber using Ar for 3 seconds and then the ALD process was performed to form the TiO x electron collector layer on the substrate.
Titanium (IV) isopropoxide was prepared as a Ti precursor when the PEALD process was used. High purity O 2 was used as the oxygen source, and high purity Ar was prepared as the carrier gas and purging gas of the Ti precursor.
The PEALD deposition cycle was pre-purged for 10 seconds, injected with a Ti precursor source for 3 seconds, followed by a 1 second high purity O 2 implantation process and then a 300 W plasma treatment.
Both processes were followed by post-purging for 10 seconds.
A TiOx electron collection layer about 0.5 A thick per deposition cycle was formed on the substrate.
FIG. 2 is a view for explaining a characteristic improvement of a metal oxide electron collecting layer based on a low temperature process having excellent electron transfer characteristics according to the present invention.
The schematic diagram on the left side of FIG. 2 shows that the electrons can not escape into the transparent conductive layer when the conventional methods (such as the sol-gel method) It is shown that the electron collecting layer based on the low temperature process formed through the present invention is formed on the transparent conductive layer / the flexible substrate so that electrons can be efficiently collected and holes can be blocked. According to the schematic diagram on the left, a low current density and a low filling rate are exhibited in the production of solar cells, thus the efficiency of the solar cell is lowered.
FIG. 3 shows XPS analysis results in the case where the electron collecting layer is formed according to the conventional method and the case where the electron collecting layer is formed according to the method of the present invention.
In the conventional method, TiO 2 electron collecting layer was formed by sol-gel method based on ethanol or butanol through high-temperature heat treatment. As shown in FIG. 3, in the low-temperature process TiO 2 developed by the present invention, Ti 3+ and Oxygen vacancies were not observed and hydroxy groups (-OH) were not detected in comparison with the other two. The Ti 3+ defects and surface OH - groups can impair the electron collecting role due to defects in the electron collecting layer where electrons move as impurities.
FIG. 4 shows a current density-voltage graph of a low-temperature process-based perovskite thin film solar cell using three types of electron collecting layers to confirm the results of FIG. As a result, a high current density (Jsc) and a high fill factor (FF) were obtained in the low temperature process TiOx produced through the present invention. This shows that the low temperature process TiOx electron collecting layer can show high efficiency through the low temperature process.
FIG. 5 is a view for optically confirming that the results described in FIGS. 2 to 4 are due to the role of the electron collecting layer, and is a result of measuring the PL life time. As a result, the PL lifetime also showed the lowest value in the low temperature process TiOx, which shows that the light generated in the perovskite absorption layer is injected quickly and effectively through the electron collection layer into the transparent electrode.
6 shows the impedance spectroscopy measurement result. As shown in FIG. 6, in the thin film perovskite solar cell to which the low temperature process TiOx was applied, the size of the impedance semicircle was the smallest, indicating that the perovskite solar cell employing the low temperature process TiOx had the least internal resistance Show.
Hereinafter, a method of manufacturing an actual solar cell using a method of manufacturing an electron collecting layer for a solar cell according to an embodiment of the present invention will be described in further detail.
FIG. 7 shows a flowchart of a method of manufacturing a solar cell according to an embodiment of the present invention.
Referring to FIG. 7, in step S710, a flexible transparent conductive substrate is prepared and a transparent electrode etching process is performed to form electrodes. In step S720, the etched transparent conductive substrate is cleaned. Then, in step S730, the transparent conductive conductive substrate is dense to collect electrons on the transparent transparent conductive substrate to form a thin metal oxide electron collecting layer. The method of forming the electron collection layer in step S 730 includes the steps of disposing a flexible substrate in a process chamber, as already described above; Preparing an electron collector precursor; Injecting the electron collector precursor into the process chamber using an inert gas; And forming an electron collector thin film layer on the flexible substrate using a low temperature vacuum process. Dissolved in 42wt% in moles dimethylformamide (dimethyformamide, DMF) at a ratio of 1: Next S In step 740, a perovskite of the substrate for this purpose in forming the light absorbing material, CH 3 NH 3 I as PbCl 2 3 The solution is spin-coated and then heat-treated at 60 to 100 ° C to form a light absorbing layer (light absorber) crystal. In step S 750, a hole transporting layer is formed. For this purpose, a hole transporting solution containing 80 mg of Spiro-MeOTAD, 8.4 μl of tBP and 51.6 μl of LiOTFSI (154 mg / ml in acetonitrile) is prepared and spin-coated . In step S760, gold or silver was deposited to a thickness of 50 nm or more at 10-6 torr to form an electrode.
The description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features presented herein.
Claims (7)
Preparing an electron collector precursor;
Injecting the electron collector precursor into the process chamber using an inert gas; And
And forming an electron collector thin film layer on the flexible substrate using a plasma enhanced atomic layer deposition (PEALD) process which is a low temperature vacuum process,
Characterized in that after the electron collector precursor is implanted, O 2 is implanted and subjected to a plasma treatment.
(EN) METHOD FOR MANUFACTURING ELECTRONIC COLLECTING LAYER FOR SOLAR BATTERY.
Characterized in that the low temperature vacuum process is carried out at a temperature of from < RTI ID = 0.0 > 50 C < / RTI &
(EN) METHOD FOR MANUFACTURING ELECTRONIC COLLECTING LAYER FOR SOLAR BATTERY.
Characterized in that the electron collector precursor is an amorphous metal oxide precursor.
(EN) METHOD FOR MANUFACTURING ELECTRONIC COLLECTING LAYER FOR SOLAR BATTERY.
Further comprising pre-purging or post-purging the process chamber with an inert gas.
(EN) METHOD FOR MANUFACTURING ELECTRONIC COLLECTING LAYER FOR SOLAR BATTERY.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100015073A (en) * | 2008-08-04 | 2010-02-12 | 한국과학기술원 | Method for manufacturing thin film transistors based on titanium oxides as active layer and thin film transistors thereof |
| KR20110069631A (en) * | 2009-12-17 | 2011-06-23 | 서울시립대학교 산학협력단 | Method for forming crystalline titanium oxide layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100015073A (en) * | 2008-08-04 | 2010-02-12 | 한국과학기술원 | Method for manufacturing thin film transistors based on titanium oxides as active layer and thin film transistors thereof |
| KR20110069631A (en) * | 2009-12-17 | 2011-06-23 | 서울시립대학교 산학협력단 | Method for forming crystalline titanium oxide layer |
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