CN105304732A - Transparent conductive oxide film preparation method and application thereof - Google Patents
Transparent conductive oxide film preparation method and application thereof Download PDFInfo
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- 238000000151 deposition Methods 0.000 claims abstract description 65
- 230000008021 deposition Effects 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 238000001039 wet etching Methods 0.000 claims abstract description 18
- 239000010408 film Substances 0.000 claims description 103
- 239000010409 thin film Substances 0.000 claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 40
- 238000005530 etching Methods 0.000 claims description 29
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 27
- 239000011787 zinc oxide Substances 0.000 claims description 20
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- 238000001035 drying Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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]
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a transparent conductive oxide film preparation method and the application thereof. The method comprises the steps that a conductive oxide is used; depositing is carried out on a surface of a substrate to form a deposition film, wherein first deposition and secondary deposition are sequentially carried out; and wet etching is carried out on the deposition film to form a transparent conductive oxide film. First deposition is carried out at the temperature of 0 to 400 DEG C. Secondary deposition is carried out at the temperature of 400 to 800 DEG C. According to the invention, the transparent conductive oxide film can be quickly and efficiently prepared; the method has the advantages of simple steps and easy and convenient operation; the prepared transparent conductive oxide film has the advantages of high light transmittance, high haze and high uniformity.
Description
Technical Field
The invention relates to the technical field of photovoltaics, in particular to a method for preparing a transparent conductive oxide film and application thereof.
Background
There is an increasing demand for green energy, particularly for widely available solar cell products, in countries around the world. With the development of the technology, solar cell users have higher requirements on the cost performance of the cell module. Photovoltaic products are diverse in types, mainly silicon-based batteries, copper indium gallium tin batteries and cadmium telluride batteries. Silicon-based cells include single crystal silicon, polycrystalline silicon, and thin film silicon cells. Among them, the thin film solar cell has the advantages of good weak light response, good high temperature effect, little shadow influence, high annual average power generation amount, perfect combination with buildings, and the like, and has the advantages of abundant raw materials required for production, little raw material consumption, short energy recovery period, little influence of the production process on the environment, suitability for mass production, and the like, thus receiving wide attention.
As an optical system, the thin-film solar cell needs to be reasonably designed for improving the utilization rate of sunlight so as to improve the conversion efficiency. Taking a thin-film silicon solar cell as an example, a front electrode Transparent Conductive Oxide (TCO) film adopted by the thin-film silicon solar cell needs to have high optical transmittance, high electrical conductivity and strong scattering capability on incident light, so that the absorption of the cell on light is improved, the photo-generated current is increased, and the conversion efficiency of the cell is improved. The transparent conductive oxide film with the textured structure is used as the front electrode of the thin-film solar cell, so that the scattering capacity of incident light can be improved, and the optical path of light in the intrinsic absorption layer is prolonged, so that the absorption of the cell to the light is improved, namely the light trapping effect. Currently, there are two main techniques for preparing transparent conductive oxide thin films: one is to directly grow a film with a textured texture by adopting a deposition process, and the other is to obtain a relatively flat transparent conductive oxide film by adopting the deposition process and then obtain the required textured texture by a post-treatment (such as wet etching). However, the above two techniques do not achieve a very desirable effect.
Thus, the technology for preparing transparent conductive oxide thin films is still in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a method for preparing a transparent conductive oxide thin film having high transmittance, high haze, or high uniformity.
The present invention has been completed based on the following findings of the inventors:
in a deposition process for directly growing textured films, which has been applied to large-scale large-area production, for example, a Low Pressure Chemical Vapor Deposition (LPCVD) process is adopted, and a ZnO film is usually deposited by using diethyl zinc (DEZ) and water as raw materials, a texture of the textured surface is naturally formed during the deposition process of the film. Meanwhile, the production cost is difficult to reduce due to the fact that raw materials are expensive, the maintenance frequency is high, and the like. In the deposition and humidification etching process, a smooth transparent conductive oxide film can be obtained by magnetron sputtering, and the textured ZnO film is prepared by subsequent wet etching. Compared with the LPCVD process, the process can independently adjust the optical and electrical properties of the film respectively and has flexible process. More importantly, the high haze textured film can be obtained on a thinner transparent conductive oxide film. However, according to the modified Thomson film (reference: O.Kluth, G.J.H ü pkes, C.Agashe, J.M ü ller, B.Rech, thinSolidfilms442,80(2003)), in order to obtain a high haze film, the temperature and pressure must be in the proper range, and even if the resistance of the magnetron sputtered large area TCO film is uniform, it is not easy to obtain a very uniform haze distribution in the subsequent wet etching process, and the non-uniformity of the haze distribution can cause the efficiency of the film battery to decrease. This is mainly due to the fact that the structure of the film itself is not completely uniform over a large area. Therefore, the inventor finds out how to obtain a film with good uniformity and reduce the cost in the preparation of a large-area textured transparent conductive oxide film by a deposition and etching technology, and is a technical problem to be solved in the field. In order to overcome the defects in the prior art, the inventor of the invention provides a method for depositing double-layer transparent conductive oxide films at different temperatures through a great deal of exploration and repeated experimental verification, and prepares the transparent conductive oxide film with good uniformity, high transmittance and high haze by using diluted acid-base salt etching.
In view of the above, in one aspect of the present invention, there is provided a method for preparing a transparent conductive oxide thin film. According to an embodiment of the invention, the method comprises: (1) performing a deposition process on one surface of the substrate using a conductive oxide to form a deposition film, the deposition process including a primary deposition and a secondary deposition which are sequentially performed; and (2) performing wet etching on the deposited film to form a transparent conductive oxide film, wherein the first deposition is performed at a temperature of 0-400 ℃, and the second deposition is performed at a temperature of 400-800 ℃. The inventor finds that the transparent conductive oxide film can be quickly and effectively prepared and obtained by the method, the steps are simple, the operation is easy, convenient and quick, and meanwhile, the prepared transparent conductive oxide film not only has high light transmittance and high haze, but also has high uniformity, namely, the resistance and haze distribution uniformity are high, so that when the prepared transparent conductive oxide film is applied to a thin-film solar cell, the absorption of the cell to light can be improved, the photoproduction current can be increased, and the cell conversion efficiency can be improved.
According to an embodiment of the present invention, before performing step (1), the substrate is previously subjected to a cleaning process including: cleaning the substrate by using a cleaning agent; rinsing the cleaned substrate with pure water; and drying the rinsed substrate.
According to an embodiment of the invention, the first deposition and the second deposition are performed by a magnetron sputtering method, optionally the magnetron sputtering method is dc magnetron sputtering, medium frequency magnetron sputtering or radio frequency magnetron sputtering.
According to an embodiment of the present invention, the conductive oxide is at least one selected from the group consisting of aluminum-doped zinc oxide, fluorine-doped tin oxide, tin-doped indium oxide, boron-doped zinc oxide.
According to the embodiment of the invention, the first deposition is carried out at the temperature of 10-300 ℃, preferably 15-30 ℃, and the second deposition is carried out at the temperature of 450-600 ℃, preferably 480 ℃.
According to the embodiment of the invention, the time of the primary deposition is 2-10 minutes, preferably 4 minutes, and the time of the secondary deposition is 5-15 minutes, preferably 8 minutes.
According to an embodiment of the invention, the substrate is a glass substrate, preferably a semi-tempered glass substrate.
According to the embodiment of the invention, the thickness of the deposited film is 0.3-2.0 microns, and preferably 1.0 micron.
According to an embodiment of the present invention, in the step (3), an inorganic acid solution, an alkali solution, or a salt solution is used as the etching solution, and optionally, the etching solution is at least one selected from phosphoric acid, acetic acid, or 0.5 vol% hydrochloric acid.
According to the embodiment of the invention, in the step (3), the time of the wet etching is 30 to 90 seconds, preferably 60 seconds.
In another aspect of the invention, the invention provides a thin film solar cell. According to an embodiment of the present invention, the thin film solar cell includes: a front glass; a front electrode transparent conductive oxide film; a photoelectric conversion layer; a back electrode transparent conductive film; a back reflector layer; packaging materials; and a back electrode, wherein the front electrode transparent conductive oxide thin film is prepared by the method for preparing a transparent conductive oxide thin film as described above. The inventor finds that the thin-film solar cell according to the embodiment of the invention has higher light utilization rate and conversion efficiency, and mainly because the transparent conductive oxide thin film prepared by the method for preparing the transparent conductive oxide thin film is adopted as the front electrode, the thin-film solar cell has higher light transmission rate and haze, and the resistance and the haze are uniformly distributed, so that the scattering capacity of incident light can be improved, the optical path of light in the intrinsic absorption layer is prolonged, the absorption of the cell on the light is improved, and the purpose of improving the conversion efficiency of the cell is achieved.
Drawings
FIG. 1 shows a schematic flow diagram of a method for preparing a transparent conductive oxide thin film according to an embodiment of the present invention;
FIG. 2 shows a schematic flow diagram of a method of preparing a transparent conductive oxide thin film according to an embodiment of the present invention;
FIG. 3 is a graph showing the results of unevenness detection of a transparent conductive oxide thin film according to an embodiment of the present invention;
FIG. 4 is a graph showing the transmittance test results of the transparent conductive oxide thin film according to the embodiment of the present invention;
FIG. 5 is a graph showing haze measurements of transparent conductive oxide films according to embodiments of the present invention;
fig. 6 is a graph showing the sheet resistance and haze measurements of the transparent conductive oxide thin film according to the embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, the present invention provides a method of preparing a transparent conductive oxide thin film. According to an embodiment of the invention, referring to fig. 1 and 2, the method comprises the steps of:
s100: a deposition process is performed on one surface of the substrate 10 using a conductive oxide to form a deposited film 20. Therefore, the conductive oxide film 20 with a large area and a smooth surface can be quickly and effectively deposited on the substrate 10, and the formed conductive film 20 has good uniformity, which is beneficial to improving the use effect.
According to an embodiment of the present invention, the substrate 10 may be previously subjected to a cleaning process before the deposition process is performed. Specifically, the cleaning process may include: cleaning the substrate 10 with a cleaning agent; rinsing the cleaned substrate 10 with pure water; and drying the rinsed substrate 10. The type of the adopted cleaning agent is not particularly limited, and the cleaning agent can be a cleaning agent commonly used in the semiconductor industry. Therefore, organic stains, dust and other impurities on the surface of the substrate can be removed quickly and effectively, impurities can be prevented from being introduced in the subsequent steps, and the physical and chemical properties of the prepared transparent conductive oxide film can be improved.
According to the embodiment of the invention, the deposition treatment comprises a primary deposition and a secondary deposition which are sequentially carried out, wherein the primary deposition is carried out at the temperature of 0-400 ℃, and the secondary deposition is carried out at the temperature of 400-800 ℃. The inventor surprisingly finds that the distribution uniformity of the deposited film 20 can be greatly improved by depositing the deposited film 20 twice at different temperatures, the unevenness of the obtained deposited film 20 is lower than 5%, and the hardness of the formed film is higher when the secondary deposition is carried out at a higher temperature, so that the etching speed can be controlled in the subsequent etching step, the transparent conductive oxide film with uniform haze distribution can be obtained, and further, the conversion efficiency can be effectively improved when the prepared transparent conductive oxide film is applied to a thin-film solar cell.
According to an embodiment of the present invention, the primary deposition and the secondary deposition are performed by a magnetron sputtering method. Therefore, the deposited film 20 with large area and smooth surface can be effectively formed, and the operation is simple and convenient. The magnetron sputtering power can be 100W-250W, and the pressure is 2-10mTorr, thereby being beneficial to improving the flatness, uniformity and overall performance of the deposited film. According to some embodiments of the invention, the magnetron sputtering method may be direct current magnetron sputtering, intermediate frequency magnetron sputtering or radio frequency magnetron sputtering. The working principle of magnetron sputtering is that electrons collide with argon atoms in the process of flying to a substrate under the action of an electric field E, so that Ar positive ions and new electrons are generated by ionization, the new electrons fly to the substrate, the Ar positive ions accelerate flying to a cathode target under the action of the electric field and bombard the surface of the target at high energy, so that the target material is sputtered, neutral target atoms or molecules in sputtered particles are deposited on the substrate to form a thin film, and the magnetron sputtering device can be used for preparing various materials such as metal, semiconductors, insulators and the like, and has the advantages of simple equipment, easiness in control, large film coating area, strong adhesive force, high speed, low temperature, low damage and the like. The direct current magnetron sputtering utilizes direct current glow discharge, the initial electrons accelerate and collide Ar to form argon ions and other electrons (alpha process), the argon ions accelerate and collide a cathode (target material) under the action of an electric field to form secondary electron emission (gamma process), and the discharge enters a glow discharge stage after reaching stability. The radio frequency magnetron sputtering utilizes radio frequency discharge, charged particles oscillate back and forth between electrodes and collide with each other for ionization, and the electrodes can maintain discharge without contacting with plasma. The medium-frequency magnetron sputtering refers to medium-frequency reactive sputtering, and the frequency range of sputtering voltage is in the range of 10-80 KHz, so the medium-frequency magnetron sputtering is called as medium-frequency sputtering.
According to the embodiment of the invention, the first deposition can be carried out at the temperature of 10-300 ℃, and preferably at the temperature of 15-30 ℃. Therefore, the conductive oxide film with large area and high uniformity can be effectively formed, and the subsequent steps can be favorably carried out. If the primary deposition temperature is too high, energy consumption is wasted, the deposition is preferably carried out at the temperature of 15-30 ℃, the deposition can be directly carried out at room temperature under normal conditions, the substrate does not need to be additionally heated, the energy consumption can be effectively reduced, and the operation steps are simplified. According to the embodiment of the invention, the secondary deposition is carried out at the temperature of 450-600 ℃, and preferably, at the temperature of 480 ℃. Therefore, the film formed by secondary deposition has good uniformity and higher hardness, and is beneficial to controlling the etching speed in the subsequent steps so as to form the uniformly distributed high-haze conductive oxide film. If the temperature of the secondary deposition is too low, the effect of improving the hardness of the secondary deposition film cannot be achieved, the deposited film cannot have uniformly distributed haze in the subsequent steps, and if the temperature is too high, energy consumption waste is caused, and the economy is not high. The secondary deposition is carried out at the temperature of 450-600 ℃, preferably 480 ℃, so that the performance of the deposited film can be ensured, and the economic efficiency is good.
According to the embodiment of the invention, the time of the first deposition can be 2-10 minutes, preferably 4 minutes, and the time of the second deposition can be 5-15 minutes, preferably 8 minutes. Therefore, the prepared deposition film has proper thickness, and is beneficial to improving the light transmittance, the haze and the uniformity of the transparent conductive oxide film.
The specific kind of the substrate 10 is not particularly limited and may be any substrate known in the art according to an embodiment of the present invention. In the embodiment of the present invention, the substrate 10 may be a glass substrate, and preferably, may be a semi-tempered glass substrate. Therefore, the substrate 10 has high light transmittance and good high temperature resistance, and can be effectively deposited with a thin film by a magnetron sputtering method or the like.
According to the embodiment of the present invention, after the deposition process, the thickness of the deposited film 20 formed on the substrate 10 may be 0.3 to 2.0 micrometers, and preferably 1.0 micrometer. Thus, the deposited thin film 20 not only has a high light transmittance, but also has a high haze by etching in a subsequent step without affecting other properties of the deposited thin film 20.
The specific kind of the conductive oxide is not particularly limited according to an embodiment of the present invention, and may be selected by those skilled in the art according to actual needs. In some embodiments of the present invention, the conductive oxide may be at least one selected from the group consisting of aluminum-doped zinc oxide, fluorine-doped tin oxide, tin-doped indium oxide, and boron-doped zinc oxide. Therefore, the prepared deposited film 20 has high uniformity, smooth surface and high light transmittance, and the use performance of the transparent conductive oxide film is favorably improved by adopting the conductive oxide.
S200: the deposited film is wet etched to form a transparent conductive oxide film.
In this step, the surface of the deposition film 20 can form a textured texture by performing wet etching on the deposition film 20, so that the obtained transparent conductive oxide film has high light transmittance and high haze with uniform distribution, thereby improving the conversion efficiency of the thin film solar cell using the transparent conductive oxide film. Specifically, since the deposition film 20 is formed by the primary deposition and the secondary deposition which are sequentially performed, and the secondary deposition is performed at a higher temperature, the hardness of the formed film is greater, therefore, the hardness of the surface of the deposited film 20 obtained by the deposition treatment, which is away from the substrate, is high, the hardness of the surface, which is close to the substrate, is low, in the wet etching process, the etching rate of the part of the deposited film 20 far away from the substrate (i.e. the film formed by the secondary deposition) is slower, the etching rate of the part close to the substrate (i.e. the film formed by the primary deposition) is faster, the deposition of the thin film 20 is controlled by its particular structure, etch rate, combined with the crystallographic orientation of the conductive oxide, a depression having an opening angle of about 120 degrees (angle α shown in fig. 2) may be formed on the surface of the deposited film 20 away from the substrate, so that the resulting transparent conductive oxide film has a uniformly distributed high haze.
According to an embodiment of the present invention, in step S200, the specific type of the etching solution used is not particularly limited, and those skilled in the art can flexibly select the etching solution according to actual situations. In some embodiments of the present invention, an inorganic acid solution, an alkali solution, or a salt solution may be used as the etching solution. Therefore, the textured texture can be quickly and effectively formed on the surface of the deposited film, so that the obtained transparent conductive oxide film has high haze with uniform distribution. Preferably, the etching solution may be at least one selected from phosphoric acid, acetic acid, and 0.5 vol% hydrochloric acid. Therefore, the etching effect is good, the efficiency is high, and the formed texture is uniformly distributed.
According to an embodiment of the invention, in the step S200, the wet etching time may be 30-90 seconds. Therefore, the suede texture meeting the requirements can be effectively obtained. Preferably, the etching time may be 60 seconds. Therefore, texture of the suede obtained by etching is uniformly distributed, and the obtained transparent conductive oxide film has high haze which is uniformly distributed.
The inventor finds that the transparent conductive oxide film can be quickly and effectively prepared and obtained by the method, the steps are simple, the operation is easy, convenient and quick, and meanwhile, the prepared transparent conductive oxide film not only has higher light transmittance and high haze, but also has higher uniformity, namely, the resistance and the haze distribution uniformity are higher, so that when the prepared transparent conductive oxide film is applied to a thin-film solar cell, the absorption of the cell to light can be improved, the photoproduction current can be increased, and the cell conversion efficiency can be improved.
In another aspect of the invention, the invention provides a thin film solar cell. According to an embodiment of the present invention, the thin film solar cell includes: a front glass; a front electrode transparent conductive oxide film; a photoelectric conversion layer; a back electrode transparent conductive film; a back reflector layer; packaging materials; and a back electrode, wherein the front electrode transparent conductive oxide thin film is prepared by the method for preparing a transparent conductive oxide thin film as described above. The inventor finds that the thin-film solar cell according to the embodiment of the invention has higher light utilization rate and conversion efficiency, and mainly because the transparent conductive oxide thin film prepared by the method for preparing the transparent conductive oxide thin film is adopted as the front electrode, the thin-film solar cell has higher light transmission rate and haze, and the resistance and the haze are uniformly distributed, so that the scattering capacity of incident light can be improved, the optical path of light in the intrinsic absorption layer is prolonged, the absorption of the cell on the light is improved, and the purpose of improving the conversion efficiency of the cell is achieved.
The following describes embodiments of the present invention in detail.
Example 1:
in this example, a transparent conductive oxide thin film was prepared as follows:
1. cleaning a 1.3m x 1.1m ultra-white float glass substrate by using a common cleaning agent in the semiconductor industry, removing organic stains and dust on the surface of the substrate, cleaning the substrate by using pure water, and drying.
2. By adopting a magnetron sputtering method, aluminum-doped zinc oxide (ZnO: Al) is deposited on a substrate for 4min at the temperature of 25 ℃, then the temperature of the substrate is increased to 480 ℃, and secondary deposition is carried out for 8min, so that the large-area ZnO: Al transparent conductive film with the thickness of about 1000nm is obtained.
3. And (3) carrying out chemical wet etching treatment on the ZnO/Al transparent conductive film with the area of 1.1m multiplied by 1.3m obtained in the step in wet etching equipment, wherein the etching solution is 0.5% of dilute hydrochloric acid, the etching temperature is 25 ℃ and the etching time is 60s, so as to obtain the transparent conductive oxide film.
4. The thickness and the sheet resistance of the transparent conductive oxide film are tested by an XY-Table test platform by using a four-probe tester, so that the unevenness of the obtained transparent conductive oxide film is shown in figure 3, and the unevenness of the prepared transparent conductive oxide film is 5% as can be seen from figure 3.
Example 2
The transparent conductive oxide film is prepared according to the following steps:
1. cleaning a 1.3m x 1.1m ultra-white float glass substrate by using a common cleaning agent in the semiconductor industry, removing organic stains and dust on the surface of the substrate, cleaning the substrate by using pure water, and drying.
2. By adopting a magnetron sputtering method, aluminum-doped zinc oxide (ZnO: Al) is deposited on a substrate for 4min at the temperature of 25 ℃, then the temperature of the substrate is increased to 480 ℃, and secondary deposition is carried out for 8min, so that the large-area ZnO: Al transparent conductive film with the thickness of about 1000nm is obtained.
3. And (3) carrying out chemical wet etching treatment on the ZnO/Al transparent conductive film with the area of 1.1m multiplied by 1.3m obtained in the step in wet etching equipment, wherein the etching solution is 0.5% of dilute hydrochloric acid, the etching temperature is 25 ℃, and wet etching is respectively carried out for 60s and 80s to obtain the transparent conductive oxide film.
4. The transmittance, the absorptivity and the reflectivity of the transparent conductive oxide film are tested by a spectrophotometer, the Haze (Haze) is obtained by further calculation, the transmittance detection result is shown in figure 4, the Haze result is shown in figure 5, and as can be seen from figures 4 and 5, the transmittance at 600nm of the transparent conductive oxide film prepared at different etching times is more than 80%, and the Haze is more than 60%.
Example 3
The transparent conductive oxide film is prepared according to the following steps:
1. cleaning a 1.3m x 1.1m ultra-white float glass substrate by using a common cleaning agent in the semiconductor industry, removing organic stains and dust on the surface of the substrate, cleaning the substrate by using pure water, and drying.
2. By adopting a magnetron sputtering method, aluminum-doped zinc oxide (ZnO: Al) is deposited on a substrate for 4min at the temperature of 250 ℃, then the temperature of the substrate is increased to 480 ℃, and secondary deposition is carried out for 8min, so that the large-area ZnO: Al transparent conductive film with the thickness of about 1000nm is obtained.
3. And (3) carrying out chemical wet etching treatment on the ZnO/Al transparent conductive film with the area of 1.1m multiplied by 1.3m obtained in the step in wet etching equipment, wherein the etching solution is 0.5% of dilute hydrochloric acid, the etching temperature is 25 ℃, and the etching time is 60s, so as to obtain the transparent conductive oxide film.
4. The sheet resistance of the transparent conductive oxide film prepared in the above steps was measured by a four-probe test apparatus and the Haze (Haze) was calculated by measuring the transmittance, absorptance and reflectance, as shown in fig. 6, and as can be seen from fig. 6, the sheet resistance of the transparent conductive oxide film prepared was less than 20 ohm, and the Haze was > 40%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of preparing a transparent conductive oxide film, comprising:
(1) performing a deposition process on one surface of the substrate using a conductive oxide, the deposition process including a primary deposition and a secondary deposition which are sequentially performed, so as to form a deposited film; and
(2) performing wet etching on the deposited film to form the transparent conductive oxide film,
wherein,
the primary deposition is carried out at a temperature of 0-400 ℃, and
the secondary deposition is carried out at a temperature of 400-800 ℃.
2. The method according to claim 1, wherein before performing step (1), the substrate is subjected to a cleaning process in advance, the cleaning process comprising:
cleaning the substrate by using a cleaning agent;
rinsing the cleaned substrate with pure water; and
and drying the rinsed substrate.
3. The method according to claim 1, characterized in that the primary deposition and the secondary deposition are carried out by a magnetron sputtering method,
optionally, the magnetron sputtering method is direct current magnetron sputtering, medium frequency magnetron sputtering or radio frequency magnetron sputtering.
4. The method according to claim 1, wherein the conductive oxide is at least one selected from the group consisting of aluminum-doped zinc oxide, fluorine-doped tin oxide, tin-doped indium oxide, and boron-doped zinc oxide.
5. A method according to claim 1, characterized in that the primary deposition is carried out at a temperature of 10-300 degrees Celsius, preferably 15-30 degrees Celsius,
the secondary deposition is carried out at a temperature of 450-600 ℃, preferably 480 ℃.
6. The method according to claim 1, wherein the time of the first deposition is 2-10 minutes, preferably 4 minutes,
the time of the secondary deposition is 5-15 minutes, and preferably 8 minutes.
7. Method according to claim 1, characterized in that the substrate is a glass substrate, preferably a semi-tempered glass substrate.
8. The method according to claim 1, wherein the deposited film has a thickness of 0.3 to 2.0 micrometers, preferably 1.0 micrometer.
9. The method according to claim 1, wherein in step (2), an inorganic acid solution, an alkali solution or a salt solution is used as the etching solution,
optionally, the etching solution is at least one selected from phosphoric acid, acetic acid or 0.5 vol% hydrochloric acid,
optionally, in the step (2), the time of the wet etching is 30 to 90 seconds, preferably 60 seconds.
10. A thin film solar cell, comprising:
a front glass;
a front electrode transparent conductive oxide film;
a photoelectric conversion layer;
a back electrode transparent conductive film;
a back reflector layer;
packaging materials; and
a back electrode, which is provided on the back side,
wherein the front electrode transparent conductive oxide thin film is prepared by the method of any one of claims 1 to 9.
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| CN101697289A (en) * | 2009-10-15 | 2010-04-21 | 浙江大学 | Transparent conducting film and preparation method thereof |
| CN101820003A (en) * | 2010-04-27 | 2010-09-01 | 南开大学 | Doubles-layer zinc oxide transparent and conductive film for film solar cell and preparation method thereof |
| CN103681892A (en) * | 2012-09-18 | 2014-03-26 | 台积太阳能股份有限公司 | Solar cell |
| US20140083501A1 (en) * | 2011-09-28 | 2014-03-27 | Korea Institute Of Energy Research | Transparent conducting film having double structure and method of manufacturing the same |
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| CN101697289A (en) * | 2009-10-15 | 2010-04-21 | 浙江大学 | Transparent conducting film and preparation method thereof |
| CN101820003A (en) * | 2010-04-27 | 2010-09-01 | 南开大学 | Doubles-layer zinc oxide transparent and conductive film for film solar cell and preparation method thereof |
| US20140083501A1 (en) * | 2011-09-28 | 2014-03-27 | Korea Institute Of Energy Research | Transparent conducting film having double structure and method of manufacturing the same |
| CN103681892A (en) * | 2012-09-18 | 2014-03-26 | 台积太阳能股份有限公司 | Solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111560602A (en) * | 2020-04-13 | 2020-08-21 | 哈尔滨工业大学 | Optimization method for surface recombination of oxide film |
| CN111560602B (en) * | 2020-04-13 | 2021-10-26 | 哈尔滨工业大学 | Optimization method for surface recombination of oxide film |
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