CN111446149A - Method for preparing transparent conductive oxide film - Google Patents

Method for preparing transparent conductive oxide film Download PDF

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CN111446149A
CN111446149A CN201811636224.6A CN201811636224A CN111446149A CN 111446149 A CN111446149 A CN 111446149A CN 201811636224 A CN201811636224 A CN 201811636224A CN 111446149 A CN111446149 A CN 111446149A
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layer
film
tco
oxygen
less
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崔鸽
董刚强
李沅民
谭钦
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Deyun Chuangxin (Beijing) Technology Co.,Ltd.
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Beijing Juntai Innovation Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02697—Forming conducting materials on a substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/548—Controlling the composition
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1876—Particular processes or apparatus for batch treatment of the devices
    • 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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    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention provides a preparation method of a transparent conductive oxide film, which comprises the following steps: depositing according to a first preset condition and a first preset time to obtain a first layer of sub TCO film, wherein the first preset condition comprises a first oxygen-argon ratio; and depositing on the first layer of sub-TCO film according to a second preset condition and a second preset time to obtain a second layer of sub-TCO film, wherein the second preset condition comprises a second oxygen-argon ratio which is greater than the first oxygen-argon ratio. Because the oxygen-argon ratio when the second layer of TCO film is deposited is larger than that when the first layer of TCO film is deposited, the TCO film formed by the first layer of TCO film and the second layer of TCO film can have better optical performance and electrical performance, and the photoelectric conversion efficiency of the solar cell using the TCO film can be improved.

Description

Method for preparing transparent conductive oxide film
Technical Field
The invention relates to a preparation method of a solar cell chip, in particular to a preparation method of a Transparent Conductive Oxide (TCO) film.
Background
With the increasing shortage of renewable resources, solar cells are receiving extensive attention and research. The TCO film is an important component of a solar cell such as an amorphous silicon/crystalline silicon heterojunction solar cell (Hetero-junction with Intrinsic Thin layer abbreviated as HJT) or a Thin-film solar cell, and when the TCO film is applied to the solar cell, the TCO film mainly plays a role in collecting current and transmitting light, so that the optical performance and the electrical performance of the TCO film directly influence the photoelectric conversion efficiency of the solar cell.
The optical performance and the electrical performance of the TCO film used in the prior art generally have a trade-off relationship, that is, the better optical performance and the better electrical performance cannot be considered at the same time, so that the photoelectric conversion efficiency of the solar cell using the TCO film is poor.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a TCO film, and the TCO film used in the prior art cannot give consideration to both good optical performance and good electrical performance, so that the problem of poor photoelectric conversion efficiency of a solar cell using the TCO film is caused.
In order to solve the technical problem, the invention is realized as follows:
the embodiment of the invention provides a preparation method of a TCO film, which comprises the following steps:
depositing according to a first preset condition and a first preset time to obtain a first layer of sub TCO film, wherein the first preset condition comprises a first oxygen-argon ratio;
and depositing on the first layer of sub-TCO film according to a second preset condition and a second preset time to obtain a second layer of sub-TCO film, wherein the second preset condition comprises a second oxygen-argon ratio which is greater than the first oxygen-argon ratio.
Optionally, the first sub-TCO film is any one of an Indium Tin Oxide (ITO) film and a zirconium-doped Indium Tin Oxide (ITO: Zr) film, and the second sub-TCO film is an ITO film and an ITO: any one of Zr thin films;
when the first layer of sub-TCO film and the second layer of sub-TCO film are both ITO films, the first oxygen-argon ratio is greater than or equal to 1% and less than 3%, and the second oxygen-argon ratio is greater than or equal to 7% and less than 9%;
when the first layer of sub-TCO film and the second layer of sub-TCO film are both ITO: in the case of the Zr thin film, the first oxygen-argon ratio is more than or equal to 0.5% and less than 1%, and the second oxygen-argon ratio is more than or equal to 2% and less than 2.5%.
Optionally, the first preset condition further comprises that the background vacuum degree reaches at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the first preset time is more than 0 and less than or equal to 5 minutes;
the second preset condition further comprises that the background vacuum degree reaches at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the second preset time is greater than 0 and less than or equal to 5 minutes.
Optionally, the preparation method of the TCO film further includes:
depositing on the first layer of sub-TCO film according to a third preset condition and a third preset time before the step of obtaining the second layer of sub-TCO film to obtain a third layer of sub-TCO film, wherein the third preset condition comprises a third oxygen-argon ratio which is greater than the first oxygen-argon ratio and less than the second oxygen-argon ratio;
and depositing on the third layer of sub-TCO film according to the second preset condition and the second preset time after the step of obtaining the third layer of sub-TCO film to form the second layer of sub-TCO film.
Optionally, the third layer of sub-TCO film is an ITO film or an ITO: any one of Zr thin films;
when the third layer of sub-TCO film is an ITO film, the third oxygen-argon ratio is greater than or equal to 3% and less than 7%;
when the third layer of sub-TCO film is ITO: in the case of the Zr thin film, the third oxygen-argon ratio is more than or equal to 1% and less than 2%.
Optionally, the third preset condition further includes that the background vacuum degree reaches at least 9 × 10-4Pa, the range of the process power is more than 0 and less than 15kW, the range of the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the third predetermined time is greater than or equal to 1.5 minutes and less than or equal to 3 minutes.
Optionally, the preparation method of the TCO film further includes:
depositing on the first layer of sub TCO film according to a fourth preset condition and a fourth preset time to obtain a first layer of transition TCO film, wherein the fourth preset condition comprises a fourth oxygen-argon ratio which is greater than the first oxygen-argon ratio;
depositing on the first transition TCO thin film layer according to a fifth preset condition and according to a fifth preset time to obtain a second transition TCO thin film layer, wherein the fifth preset condition comprises a fifth oxygen-argon ratio which is larger than the fourth oxygen-argon ratio and smaller than the second oxygen-argon ratio;
forming the third sub-TCO film from the first transition TCO film layer and the second TCO film layer;
and after the step of obtaining the second transitional TCO film layer, depositing on the second transitional TCO film layer according to the second preset condition and the second preset time to form the second sub-TCO film layer.
Optionally, the first transition TCO thin film layer is an ITO thin film layer and ITO: any one of the Zr thin film layers, the second transition TCO thin film layer is an ITO thin film layer and ITO: any one of the Zr thin film layers;
when the first transition TCO thin film layer and the second transition TCO thin film layer are ITO thin film layers, the fourth oxygen-argon ratio is greater than or equal to 3% and less than 5%, and the fifth oxygen-argon ratio is greater than or equal to 5% and less than 7%;
when the first transition TCO thin film layer and the second transition TCO thin film layer are both ITO: in the case of the Zr thin film layer, the fourth oxygen/argon ratio is 1% or more and less than 1.5%, and the fifth oxygen/argon ratio is 1.5% or more and less than 2%.
Optionally, the fourth preset condition further includes that the background vacuum degree reaches at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the range of the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the fourth preset time is greater than or equal to 0.5 minutes and less than or equal to 2 minutes;
the fifth preset condition further comprises that the background vacuum degree at least reaches 9 × 10-4Pa, the range of the process power is more than 0 and less than 15kW, the range of the deposition rate is more than 0 and less than 1.5nm/s, and the range of the pressure intensity is more than or equal to 0.2Pa and less than 0.8 Pa;
the fifth predetermined time is greater than or equal to 0.5 minutes and less than or equal to 2 minutes.
Optionally, the preparation method of the TCO film further includes:
before the step of obtaining the first layer of sub-TCO film, depositing according to a sixth preset condition and a sixth preset time to obtain a fourth layer of sub-TCO film, wherein the sixth preset condition comprises a sixth oxygen-argon ratio which is more than 0 and less than the first oxygen-argon ratio;
and depositing on the fourth layer of sub-TCO film according to the first preset condition and the first preset time after the step of obtaining the fourth layer of sub-TCO film to form the first layer of sub-TCO film.
Optionally, the fourth sub-TCO film is an ITO film or an ITO: any one of Zr thin films;
when the fourth sub-TCO film is an ITO film, the sixth oxygen-argon ratio is greater than 0 and less than 1%;
when the fourth sub-TCO film is ITO: in the case of the Zr thin film, the sixth oxygen-argon ratio is more than 0 and less than 0.5%.
Optionally, the sixth preset condition further includes that the background vacuum degree reaches at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the sixth predetermined time is greater than or equal to 0.5 minutes and less than or equal to 2 minutes.
Optionally, the argon flow rate is the same when the first layer of sub-TCO film, the second layer of sub-TCO film, the third layer of sub-TCO film and the fourth layer of sub-TCO film are deposited.
The embodiment of the invention has the following beneficial technical effects:
when the TCO film is prepared, the increase of oxygen can lead to the reduction of oxygen vacancy and carrier concentration in the TCO film, so that the sheet resistance of the TCO film is increased and the permeation is increased, further the electrical property of the TCO film is reduced and the optical property is improved, namely the electrical property of the TCO film prepared under the condition of less oxygen introduction is better, and the optical property of the TCO film prepared under the condition of more oxygen introduction is better. In the embodiment of the invention, as the second oxygen-argon ratio is greater than the first oxygen-argon ratio, namely the oxygen-argon ratio when the second layer of TCO film is deposited is greater than the oxygen-argon ratio when the first layer of TCO film is deposited, the optical performance of the second layer of TCO film is better than that of the first layer of TCO film, and the electrical performance of the first layer of TCO film is better than that of the second layer of TCO film, so that the TCO film formed by the first layer of TCO film and the second layer of TCO film can have better optical performance and better electrical performance at the same time, and the photoelectric conversion efficiency of the solar cell using the TCO film can be improved.
Drawings
Fig. 1 is a flowchart illustrating a method for manufacturing a TCO film according to an embodiment of the present invention.
Fig. 2 is a second flowchart of a method for manufacturing a TCO film according to an embodiment of the present invention.
Fig. 3 is a third flowchart of a method for manufacturing a TCO film according to an embodiment of the present invention.
Fig. 4 is a fourth flowchart of a method for manufacturing a TCO film according to an embodiment of the present invention.
Fig. 5 is a diagram illustrating an example of a method for fabricating a TCO film according to an embodiment of the present invention.
Fig. 6 is a second example of a method for preparing a TCO film according to an embodiment of the present invention.
Fig. 7 is a third example of a method for preparing a TCO film according to an embodiment of the present invention.
Fig. 8 is a fourth example of a method for preparing a TCO film according to an embodiment of the present invention.
Fig. 9 is a fifth exemplary illustration showing a method for fabricating a TCO film according to an embodiment of the present invention.
Fig. 10 is a sixth example of a method for preparing a TCO film according to an embodiment of the present invention.
Fig. 11 is a seventh exemplary diagram illustrating a method of fabricating a TCO film according to an embodiment of the present invention.
Fig. 12 is an example of an eighth embodiment of a method for fabricating a TCO film according to the present invention.
FIG. 13 is a ninth illustration showing an example of a method for preparing a TCO film according to an embodiment of the invention.
FIG. 14 is a diagram illustrating an example of a method for fabricating a TCO film according to an embodiment of the invention.
Fig. 15 is an eleventh exemplary diagram of a method for manufacturing a TCO film according to an embodiment of the present invention.
FIG. 16 is a diagram illustrating a method of fabricating a TCO film according to an embodiment of the invention.
Fig. 17 is a thirteen example of a method for manufacturing a TCO film according to an embodiment of the present invention.
Fig. 18 is a fourteenth exemplary diagram illustrating a method for fabricating a TCO film according to an embodiment of the present invention.
Fig. 19 is a fifteenth illustration showing a method for fabricating a TCO film according to an embodiment of the present invention.
Fig. 20 is a sixteenth exemplary diagram of a method for fabricating a TCO film according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, an embodiment of the invention provides a method for preparing a TCO film, including:
step S101, depositing according to a first preset condition and a first preset time to obtain a first layer of sub TCO film, wherein the first preset condition comprises a first oxygen-argon ratio;
step S102, depositing on the first layer of sub-TCO film according to a second preset condition and a second preset time to obtain a second layer of sub-TCO film, wherein the second preset condition comprises a second oxygen-argon ratio, and the second oxygen-argon ratio is larger than the first oxygen-argon ratio.
The first preset time may be greater than 0 and less than or equal to 5 minutes, for example, 1 minute, 2 minutes or 4 minutes, and may be specifically set as needed. The second preset time may be greater than 0 and less than or equal to 5 minutes, for example, 1 minute, 1.5 minutes, 2 minutes, or 3.5 minutes, and may be specifically set as needed.
The first layer of TCO film can be specifically an ITO film or an ITO: various TCO films such as Zr film, tungsten-doped indium oxide (In2O3: W, IWO for short) film or aluminum-doped zinc oxide (ZnO: Al, AZO for short) film. The second layer of sub-TCO film can be specifically an ITO film or an ITO: various TCO films such as Zr film, IWO film or AZO film.
When the first TCO film and the second TCO film are ITO films, the first oxygen/argon ratio may be greater than or equal to 1% and less than 3%, and the second oxygen/argon ratio may be greater than or equal to 7% and less than 9%. When the first layer of sub-TCO film and the second layer of sub-TCO film are both ITO: the first oxygen/argon ratio may be 0.5% or more and less than 1% and the second oxygen/argon ratio may be 2% or more and less than 2.5% for the Zr thin film.
The first predetermined condition may further comprise a background vacuum level of at least 9 × 10-4Pa, process power greater than 0 and less than 15kW, deposition rate greater than 0 and less than 1.5nm/s, pressure greater than or equal to 0.2Pa and less than 0.8Pa, and background vacuum degree of at least 9 × 10-4Pa may be a background vacuum of between 9 × 10-4Pa and 1 × 10-4Pa, e.g. background vacuum of 5 × 10-4Pa。
The second predetermined condition may further comprise a background vacuum level of at least 9 × 10-4Pa, process power greater than 0 and less than 15kW, deposition rate greater than 0 and less than 1.5nm/s, pressure greater than or equal to 0.2Pa and less than 0.8Pa, and background vacuum degree of at least 9 × 10-4Pa may be a background vacuum of between 9 × 10-4Pa and 1 × 10-4Pa, e.g. background vacuum of 5 × 10-4Pa。
When the TCO film is prepared, the increase of oxygen can lead to the reduction of oxygen vacancy and carrier concentration in the TCO film, so that the sheet resistance of the TCO film is increased and the permeation is increased, further the electrical property of the TCO film is reduced and the optical property is improved, namely the electrical property of the TCO film prepared under the condition of less oxygen introduction is better, and the optical property of the TCO film prepared under the condition of more oxygen introduction is better. In the embodiment of the invention, as the second oxygen-argon ratio is greater than the first oxygen-argon ratio, namely the oxygen-argon ratio when the second layer of TCO film is deposited is greater than the oxygen-argon ratio when the first layer of TCO film is deposited, the optical performance of the second layer of TCO film is better than that of the first layer of TCO film, and the electrical performance of the first layer of TCO film is better than that of the second layer of TCO film, so that the TCO film formed by the first layer of TCO film and the second layer of TCO film can have better optical performance and better electrical performance at the same time, and the photoelectric conversion efficiency of the solar cell using the TCO film can be improved.
Optionally, as shown in fig. 2, the method for preparing the TCO film further includes:
step S103, before the step S102, depositing on the first layer of sub-TCO film according to a third preset condition and a third preset time to obtain a third layer of sub-TCO film, wherein the third preset condition comprises a third oxygen-argon ratio which is greater than the first oxygen-argon ratio and less than the second oxygen-argon ratio;
step S102 includes:
after step S103, depositing on the third TCO film according to a second preset condition and for a second preset time to form a second TCO film.
The third preset time may be greater than or equal to 1.5 minutes and less than or equal to 3 minutes, for example, 1.5 minutes, 2 minutes or 3 minutes, and may be specifically set as needed.
The third TCO film may be specifically an ITO film, an ITO: various TCO films such as Zr film, IWO film or AZO film. When the third TCO film is an ITO film, the third oxygen/argon ratio may be greater than or equal to 3% and less than 7%. When the third layer of sub-TCO film is ITO: in the case of the Zr thin film, the third oxygen/argon ratio may be 1% or more and less than 2%.
The third predetermined condition may further comprise a background vacuum level of at least 9 × 10-4Pa, process power greater than 0 and less than 15kW, deposition rate greater than 0 and less than 1.5nm/s, pressure greater than or equal to 0.2Pa and less than 0.8Pa, and background vacuum degree of at least 9 × 10-4Pa may be a background vacuum of between 9 × 10-4Pa and 1 × 10-4Pa, e.g. background vacuum of 5 × 10-4Pa。
The third oxygen-argon ratio is larger than the first oxygen-argon ratio and smaller than the second oxygen-argon ratio, namely the oxygen-argon ratio when the third layer of sub-TCO film is deposited is larger than the oxygen-argon ratio when the first layer of sub-TCO film is deposited and smaller than the oxygen-argon ratio when the second layer of sub-TCO film is deposited, so that the electrical property and the optical property of the third layer of sub-TCO film are both between the first TCO sub-film and the second TCO sub-film, and thus, the third layer of sub-TCO film can play a transition role between the first TCO sub-film and the second TCO sub-film, and further the comprehensive performance of the whole TCO film can be better.
Optionally, as shown in fig. 3, the method for preparing the TCO film further includes:
step S104, depositing on the first layer of TCO film according to a fourth preset condition and a fourth preset time to obtain a first layer of transition TCO film, wherein the fourth preset condition comprises a fourth oxygen-argon ratio which is larger than the first oxygen-argon ratio;
step S105, depositing the first transition TCO thin film layer according to a fifth preset condition and a fifth preset time to obtain a second transition TCO thin film layer, wherein the fifth preset condition comprises a fifth oxygen-argon ratio which is larger than a fourth oxygen-argon ratio and smaller than a second oxygen-argon ratio;
forming a third layer of sub TCO film by the first transition TCO film layer and the second TCO film layer;
step S102 includes:
after the step S105, depositing on the second transition TCO thin film layer according to a second preset condition and a second preset time, so as to form a second sub-TCO thin film.
The fourth preset time may be greater than or equal to 0.5 minute and less than or equal to 2 minutes, for example, 1 minute, 1.5 minutes, or 2 minutes, and may be specifically set as needed. The fifth preset time may be greater than or equal to 0.5 minute and less than or equal to 2 minutes, for example, 1 minute, 1.5 minutes, or 2 minutes, and may be specifically set as needed.
The first transition TCO film layer can be specifically an ITO film layer or an ITO: various TCO film layers such as a Zr film layer, an IWO film layer or an AZO film layer. The second transition TCO thin film layer may be specifically an ITO thin film layer, ITO: various TCO film layers such as a Zr film layer, an IWO film layer or an AZO film layer.
When the first transition TCO thin film layer and the second transition TCO thin film layer are ITO thin films, the fourth oxygen/argon ratio may be greater than or equal to 3% and less than 5%, and the fifth oxygen/argon ratio may be greater than or equal to 5% and less than 7%. When the first transition TCO film layer and the second transition TCO film layer are both ITO: in the case of the Zr thin film layer, the fourth oxygen/argon ratio may be 1% or more and less than 1.5%, and the fifth oxygen/argon ratio may be 1.5% or more and less than 2%.
The fourth predetermined condition may further comprise a background vacuum level of at least 9 × 10-4Pa, process power greater than 0 and less than 15kW, deposition rate greater than 0 and less than 1.5nm/s, pressure greater than or equal to 0.2Pa and less than 0.8Pa, and background vacuum degree of at least 9 × 10-4Pa may be a background vacuum of between 9 × 10-4Pa and 1 × 10-4Pa, e.g. background vacuum of 5 × 10-4Pa。
The fifth predetermined condition may further comprise a background vacuum level of at least 9 × 10-4Pa, process power greater than 0 and less than 15kW, deposition rate greater than 0 and less than 1.5nm/s, pressure greater than or equal to 0.2Pa and less than 0.8Pa, and background vacuum degree of at least 9 × 10-4Pa may be a background vacuum of between 9 × 10-4Pa and 1 × 10-4Pa, e.g. background vacuum of 5 × 10-4Pa。
The third layer of TCO film comprises two transition TCO film layers, wherein the fourth oxygen-argon ratio is greater than the first oxygen-argon ratio, the fifth oxygen-argon ratio is greater than the fourth oxygen-argon ratio and less than the second oxygen-argon ratio, namely the oxygen-argon ratio when the first transition TCO film layer is deposited is greater than the oxygen-argon ratio when the first layer of TCO film is deposited and less than the oxygen-argon ratio when the second transition TCO film layer is deposited, the oxygen-argon ratio when the second transition TCO film layer is deposited is greater than the oxygen-argon ratio when the first transition TCO film layer is deposited and less than the oxygen-argon ratio when the second transition TCO film layer is deposited, so that the electrical property and the optical property of the first transition TCO film layer are both between the first transition TCO film layer and the second transition TCO film layer, and the electrical property and the optical property of the second transition TCO film layer are both between the first transition TCO film layer and the second TCO film layer, thus the third layer of TCO film can perform layer-by-layer transition on the electrical property and the optical property, the transition between the electrical property and the optical property can be more gradual, and the comprehensive performance of the whole TCO film can be further better.
It should be noted that the third sub-TCO film may further include three or more transition TCO film layers, where each transition TCO film layer may be obtained by depositing on the previous transition TCO film layer according to different preset conditions and according to the same or different preset time.
Optionally, as shown in fig. 4, the method for preparing the TCO film further includes:
step S106, before the step S101, depositing according to a sixth preset condition and a sixth preset time to obtain a fourth layer of sub-TCO film, wherein the sixth preset condition comprises a sixth oxygen-argon ratio which is greater than 0 and smaller than the first oxygen-argon ratio;
step S101 includes:
after step S106, depositing on the fourth sub-TCO film according to a first preset condition for a first preset time to form a first sub-TCO film.
The sixth preset time may be greater than or equal to 0.5 minute and less than or equal to 2 minutes, for example, 1 minute, 1.5 minutes or 2 minutes, and may be specifically set as required.
The fourth sub-TCO film may be specifically an ITO film, an ITO: various TCO films such as Zr film, IWO film or AZO film. When the fourth sub-TCO film is an ITO film, the sixth oxygen/argon ratio may be greater than 0 and less than 1%. When the fourth sub-TCO film is ITO: the sixth oxygen/argon ratio of the Zr thin film may be more than 0 and less than 0.5%.
The sixth predetermined condition may further comprise a background vacuum level of at least 9 × 10-4Pa, process power greater than 0 and less than 15kW, deposition rate in the range of greater than 0 and less than 1.5nm/s, pressure greater than or equal toAt 0.2Pa to less than 0.8Pa, wherein the background vacuum degree reaches at least 9 × 10-4Pa may be a background vacuum of between 9 × 10-4Pa and 1 × 10-4Pa, e.g. background vacuum of 5 × 10-4Pa。
Since the fourth sub-TCO film is deposited according to the sixth preset condition before the first sub-TCO film is obtained, the fourth sub-TCO film can be used as a seed layer of the whole TCO film to be in contact with other film layers (for example, an amorphous silicon film layer) of the solar cell, so that the contact between the TCO film and the other film layers of the solar cell can be further improved, the damage to the other film layers of the solar cell is reduced, and the photoelectric conversion efficiency of the solar cell using the TCO film can be further improved.
Optionally, the flow rate of argon gas is the same when depositing the first, second, third and fourth sub-TCO films.
Optionally, the deposition mode in this application is physical vapor deposition.
Therefore, the oxygen-argon ratio during physical vapor deposition is changed by keeping the argon flow unchanged and changing the oxygen flow, so that the operation of changing the oxygen-argon ratio is simpler, and the preparation difficulty can be reduced.
The following description is given by way of example of one of the ITO films in the TCO film:
for example one
For example, in one embodiment of the present invention, the method for preparing an ITO thin film includes the following five steps:
step 501, carrying out physical vapor deposition for 1 minute according to sixth preset conditions to obtain a fourth layer of sub-ITO film, wherein the sixth preset conditions comprise that the oxygen-argon ratio is 0.3%, and the background vacuum degree is 5 × 10-4Pa, process power of 5kW, deposition rate of 0.8nm/s, and pressure of 0.48 Pa;
step 502, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the fourth layer of sub-ITO film for 1.5 minutes according to a first preset condition to obtain a first layer of sub-ITO film, wherein the first preset condition comprises the following steps: oxygen-argon ratio of 2.4%, backgroundVacuum degree of 5 × 10-4Pa, process power of 5kW, deposition rate of 0.76nm/s, and pressure of 0.5 Pa;
503, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition on the first layer of the ITO thin film for 1.5 minutes according to a fourth preset condition to obtain a first layer of a transition ITO thin film layer, wherein the fourth preset condition comprises that the oxygen-argon ratio is 4.4%, and the background vacuum degree is 5 × 10-4Pa, process power of 5kW, deposition rate of 0.74nm/s, and pressure of 0.51 Pa;
step 504, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the first transition ITO thin film layer for 1.5 minutes according to a fifth preset condition to obtain a second transition ITO thin film layer, wherein the fifth preset condition comprises that the oxygen-argon ratio is 6.4%, and the background vacuum degree is 5 × 10-4Pa, process power of 5kW, deposition rate of 0.74nm/s, and pressure of 0.51 Pa;
505, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the first layer of sub-ITO film for 1.5 minutes according to a second preset condition to obtain a second layer of sub-ITO film, wherein the second preset condition comprises that the oxygen-argon ratio is 8.4%, and the background vacuum degree is 5 × 10-4Pa, process power of 5kW, deposition rate of 0.72nm/s, and pressure of 0.53 Pa. To this end, the ITO thin film is manufactured, and the structure of the obtained ITO thin film is shown in fig. 5, as shown in fig. 5, 51 denotes a fourth layer of sub-ITO thin film, 52 denotes a first layer of sub-ITO thin film, 53 denotes a first layer of transition ITO thin film layer, 54 denotes a second layer of transition ITO thin film layer, and 55 denotes a second layer of sub-ITO thin film.
Here, in order to have a more intuitive feeling of the change of the oxygen/argon ratio during the steps 501 to 505, please refer to fig. 6. As shown in fig. 6, which is a graph of the oxygen/argon ratio as a function of the deposition time during steps 501 to 505, wherein the abscissa in fig. 6 represents the entire deposition time for preparing the ITO film, and the ordinate in fig. 6 represents the change of the oxygen/argon ratio when preparing the ITO film; it should be noted that fig. 6 shows the oxygen/argon ratio in a normalized manner, that is, the oxygen/argon ratio during step 501 (i.e., during the deposition of the fourth sub-ITO film) is 1, and the oxygen/argon ratios in other steps are all changed by taking the oxygen/argon ratio during step 501 as a reference.
The optical performance of the TCO film is usually measured by effective transmittance (TTe), TTe is T/(1-R), where T represents the transmittance of the TCO film and R represents the reflection of the TCO film, and generally, a higher TTe indicates a better optical performance of the TCO film. Fig. 7 is a graph comparing the ITO thin film prepared in this example (i.e., the ITO thin film prepared in accordance with steps 501 to 505 described above) with TTe of the ITO thin film of the prior art, in which the solid line represents TTe of the ITO thin film prepared in this example as a function of wavelength, and the dotted line represents TTe of the ITO thin film of the prior art as a function of wavelength. As can be seen from FIG. 7, in the near infrared band, TTe of the ITO thin film prepared in this example is greatly improved compared with the ITO thin film in the prior art, and especially in the long wavelength band of 1000-1200nm, the average value of TTe is improved by 1.86%. Thus, the optical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
The electrical properties of TCO films are generally measured by bulk resistance, carrier concentration and carrier mobility. As shown in table 1, which is a comparison table of the ITO thin film prepared in this example and the ITO thin film in the prior art after normalization of the sheet resistance, the carrier concentration, and the carrier mobility, it can be known from table 1 that, compared with the ITO thin film in the prior art, the sheet resistance of the ITO thin film prepared in this example is reduced by 42%, the carrier concentration is increased by nearly 2 times, and the carrier mobility is increased by more than 1 time; therefore, the electrical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
TABLE 1
Square resistor Concentration of carriers Carrier mobility
ITO film in prior art 1.00 1.00 1.00
ITO film prepared in this example 0.58 2.71 2.15
Table 2 shows a table comparing the maximum output power Pmax, the photoelectric conversion efficiency Eff, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF of the HJT cell using the ITO thin film prepared in this example with those of the HJT cell using the ITO thin film of the related art. As can be seen from table 2, compared with the HJT cell using the ITO thin film in the prior art, the open-circuit voltage Voc of the HJT cell using the ITO thin film prepared in this example is increased by 1.5%, the short-circuit current Isc is increased by 1%, the fill factor FF is increased by 4%, and finally, the maximum output power Pmax and the photoelectric conversion efficiency Eff are both increased by 6%.
TABLE 2
Figure BDA0001930107130000131
Fig. 8 is a graph comparing the External Quantum Efficiency (EQE) of the HJT cell using the ITO thin film prepared in this example with that of the HJT cell using the ITO thin film of the prior art, in which the solid line shows the change of EQE of the HJT cell using the ITO thin film prepared in this example with the wavelength, and the dotted line shows the change of EQE of the HJT cell using the ITO thin film of the prior art with the wavelength. As can be seen from fig. 8, in the near infrared band, the EQE of the ITO thin film prepared in this example is greatly improved compared with the ITO thin film in the prior art, and especially in the band above 1000nm, the EQE lifting amount reaches above 4%. Therefore, as can be seen from table 2 and fig. 8, when the ITO thin film prepared in this example is applied to an HJT cell, the performance of the HJT cell can be improved and enhanced in various aspects, and finally, the photoelectric conversion efficiency of the cell is enhanced.
Example II
For example, in another embodiment of the present invention, the method for preparing an ITO thin film includes the following five steps:
601, carrying out physical vapor deposition for 1 minute according to sixth preset conditions to obtain a fourth layer of sub-ITO film, wherein the sixth preset conditions comprise that the oxygen-argon ratio is 0.3 percent, and the background vacuum degree is 5 × 10-4Pa, process power of 1kW, deposition rate of 0.1nm/s, and pressure of 0.45 Pa;
step 602, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the fourth layer of sub-ITO film for 1.5 minutes according to a first preset condition to obtain a first layer of sub-ITO film, wherein the first preset condition comprises that the oxygen-argon ratio is 2.8%, and the background vacuum degree is 5 × 10-4Pa, process power of 4kW, deposition rate of 0.25nm/s, and pressure of 0.45 Pa;
603, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition on the first layer of the sub-ITO thin film for 1.5 minutes according to a fourth preset condition to obtain a first layer of a transition ITO thin film layer, wherein the fourth preset condition comprises that the oxygen-argon ratio is 4.2 percent, and the background vacuum degree is 5 × 10-4Pa, process power of 4kW, deposition rate of 0.24nm/s, and pressure of 0.46 Pa;
step 604, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the first transition ITO thin film layer for 1.5 minutes according to a fifth preset condition to obtain a second transition ITO thin film layer, wherein the fifth preset condition comprises that the oxygen-argon ratio is 6.2%, and the background vacuum degree is 5 × 10-4Pa, process power of 4kW, deposition rate of 0.24nm/s, and pressure of 0.46 Pa;
605, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition on the first layer of ITO film for 1.5 minutes according to a second preset conditionObtaining a second layer of ITO film, wherein the second preset condition comprises that the oxygen-argon ratio is 8.2 percent, and the background vacuum degree is 5 × 10-4Pa, process power 4kW, deposition rate 0.23nm/s, and pressure 0.47 Pa. Thus, the preparation of the ITO film is completed.
Here, in order to have a more intuitive feeling of the change of the oxygen/argon ratio during the steps 601 to 605, please refer to fig. 9. FIG. 9 is a graph showing the change of oxygen/argon ratio with respect to the deposition time during steps 601 to 605, wherein the abscissa in FIG. 9 represents the entire deposition time for preparing an ITO thin film and the ordinate in FIG. 9 represents the change of oxygen/argon ratio when preparing an ITO thin film; fig. 9 shows the oxygen/argon ratio in a normalized manner, that is, the oxygen/argon ratio during step 601 (i.e., during the deposition of the fourth sub-ITO film) is 1, and the oxygen/argon ratios in other steps are all changed with the oxygen/argon ratio during step 601 as a reference.
FIG. 10 is a graph showing the comparison of the ITO thin film prepared in this example (i.e., the ITO thin film prepared in accordance with the above-described steps 601 to 605) with TTe of the ITO thin film of the related art, in which the solid line shows the change of TTe of the ITO thin film prepared in this example with the wavelength, and the dotted line shows the change of TTe of the ITO thin film of the related art with the wavelength. As can be seen from FIG. 10, in the near infrared band, TTe of the ITO thin film prepared in this example is greatly improved compared with the ITO thin film in the prior art, and especially in the long wavelength band of 1000-1200nm, the average value of TTe is improved by 1.62%. Thus, the optical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
As shown in table 3, which is a comparison table of the ITO thin film prepared in this example and the ITO thin film in the prior art after normalization of the sheet resistance, the carrier concentration, and the carrier mobility, it can be known from table 3 that, compared with the ITO thin film in the prior art, the sheet resistance of the ITO thin film prepared in this example is reduced by 40%, and both the carrier concentration and the carrier mobility are improved by more than 1 time; therefore, the electrical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
TABLE 3
Square resistor Concentration of carriers Carrier mobility
ITO film in prior art 1.00 1.00 1.00
ITO film prepared in this example 0.6 2.32 2.03
As shown in table 4, a table comparing the maximum output power Pmax, the photoelectric conversion efficiency Eff, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF of the HJT cell using the ITO thin film prepared in this example with those of the prior art. As can be seen from table 4, compared with the HJT cell using the ITO thin film in the prior art, the open-circuit voltage Voc of the HJT cell using the ITO thin film prepared in this example is increased by 1.3%, the short-circuit current Isc is increased by 1%, the fill factor FF is increased by 3%, and finally the maximum output power Pmax and the photoelectric conversion efficiency Eff are both increased by 5%.
TABLE 4
Figure BDA0001930107130000151
Fig. 11 is a graph comparing the EQE of the HJT cell using the ITO thin film prepared in this example with that of the prior art ITO thin film, in which the solid line shows the change in EQE with wavelength of the HJT cell using the ITO thin film prepared in this example, and the dotted line shows the change in EQE with wavelength of the HJT cell using the prior art ITO thin film. As can be seen from fig. 11, in the near infrared band, the EQE of the ITO thin film prepared in this example is greatly improved compared with the ITO thin film in the prior art, and especially in the band above 1000nm, the EQE lifting amount reaches above 3.8%. Therefore, as can be seen from table 4 and fig. 11, when the ITO thin film prepared in this example is applied to an HJT cell, the performance of the HJT cell can be improved and enhanced in various aspects, and finally, the photoelectric conversion efficiency of the cell is enhanced.
Example III
For example, in another embodiment of the present invention, the method for preparing an ITO thin film includes the following four steps:
701, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition for 2.5 minutes according to a first preset condition to obtain a first layer of ITO film, wherein the first preset condition comprises that the oxygen-argon ratio is 2.3 percent, and the background vacuum degree is 5 × 10-4Pa, process power of 4.5kW, deposition rate of 0.16nm/s, and pressure of 0.45 Pa;
step 702, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition on the first layer of the sub ITO thin film for 1.5 minutes according to a fourth preset condition to obtain a first layer of a transition ITO thin film layer, wherein the fourth preset condition comprises that the oxygen-argon ratio is 3.8 percent, and the background vacuum degree is 5 × 10-4Pa, process power of 5kW, deposition rate of 0.16nm/s, and pressure of 0.45 Pa;
703, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition on the first transition ITO thin film layer for 1.5 minutes according to a fifth preset condition to obtain a second transition ITO thin film layer, wherein the fifth preset condition comprises that the oxygen-argon ratio is 5.3%, and the background vacuum degree is 5 × 10-4Pa, process power of 5kW, deposition rate of 0.16nm/s, and pressure of 0.45 Pa;
step 704, keeping the flow of argon unchangedThen, the physical vapor deposition is carried out for 1.5 minutes on the first layer of the sub-ITO film according to a second preset condition to obtain a second layer of the sub-ITO film, wherein the second preset condition comprises that the oxygen-argon ratio is 7 percent, and the background vacuum degree is 5 × 10-4Pa, process power 6kW, deposition rate 0.17nm/s, and pressure 0.45 Pa. Thus, the preparation of the ITO film is completed.
Here, in order to have a more intuitive feeling of the change of the oxygen/argon ratio during the steps 701 to 604, please refer to fig. 12. FIG. 12 is a graph showing the change of oxygen/argon ratio with respect to the deposition time during steps 701 to 704, wherein the abscissa in FIG. 12 represents the entire deposition time for preparing an ITO thin film, and the ordinate in FIG. 12 represents the change of oxygen/argon ratio when preparing an ITO thin film; it should be noted that fig. 12 shows the oxygen-argon ratio in a normalized manner, that is, the oxygen-argon ratio during step 701 (i.e., during the deposition of the first sub-ITO film) is 1, and the oxygen-argon ratios in other steps are all changed by taking the oxygen-argon ratio during step 701 as a reference.
Fig. 13 is a graph comparing the ITO thin film prepared in this example (i.e., the ITO thin film prepared in steps 701 to 704 described above) with TTe of the ITO thin film in the prior art, in which the solid line represents TTe of the ITO thin film prepared in this example as a function of wavelength, and the dotted line represents TTe of the ITO thin film in the prior art as a function of wavelength. As can be seen from FIG. 13, in the near infrared band, TTe of the ITO thin film prepared in this example is greatly improved compared with the ITO thin film in the prior art, and especially in the long wavelength band of 1000-1200nm, the average value of TTe is improved by 1.22%. Thus, the optical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
As shown in table 5, which is a comparison table of the ITO thin film prepared in this example and the ITO thin film in the prior art after the sheet resistance, the carrier concentration, and the carrier mobility are normalized, it can be known from table 5 that, compared with the ITO thin film in the prior art, the sheet resistance of the ITO thin film prepared in this example is reduced by 35%, the carrier concentration is increased by more than 1 time, and the carrier mobility is increased by nearly 1 time; therefore, the electrical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
TABLE 5
Square resistor Concentration of carriers Carrier mobility
ITO film in prior art 1.00 1.00 1.00
ITO film prepared in this example 0.65 2.04 1.96
As shown in table 6, a table comparing the maximum output power Pmax, the photoelectric conversion efficiency Eff, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF of the HJT cell using the ITO thin film prepared in this example with those of the prior art. As can be seen from table 6, compared with the HJT cell using the ITO thin film in the prior art, the open-circuit voltage Voc, the short-circuit current Isc, and the fill factor FF of the HJT cell using the ITO thin film prepared in this example are all improved, wherein the open-circuit voltage Voc is improved by 0.1%, the short-circuit current Isc is improved by 0.7%, and the fill factor FF is improved by 0.8%, and finally the maximum output power Pmax and the photoelectric conversion efficiency Eff are both improved by 1.6%.
TABLE 6
Figure BDA0001930107130000171
Fig. 14 is a graph comparing the EQE of the HJT cell using the ITO thin film prepared in this example with that of the prior art ITO thin film, in which the solid line shows the change in EQE with wavelength of the HJT cell using the ITO thin film prepared in this example, and the dotted line shows the change in EQE with wavelength of the HJT cell using the prior art ITO thin film. As can be seen from fig. 14, in the near infrared band, the EQE of the ITO thin film prepared in this example is greatly improved compared with the ITO thin film in the prior art, and especially in the band above 1000nm, the EQE lifting amount reaches above 3.6%. Therefore, as can be seen from table 6 and fig. 14, when the ITO thin film prepared in this example is applied to an HJT cell, the performance of the HJT cell can be improved and enhanced in various aspects, and finally, the photoelectric conversion efficiency of the cell is enhanced.
Example four
For example, in another embodiment of the present invention, the method for preparing an ITO thin film includes the following two steps:
step 801, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition for 2 minutes according to a first preset condition to obtain a first layer of ITO film, wherein the first preset condition comprises that the oxygen-argon ratio is 2.6%, and the background vacuum degree is 5 × 10-4Pa, process power of 4kW, deposition rate of 0.13nm/s, and pressure of 0.45 Pa;
step 802, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the first layer of sub-ITO film for 7 minutes according to a second preset condition to obtain a second layer of sub-ITO film, wherein the second preset condition comprises that the oxygen-argon ratio is 7 percent, and the background vacuum degree is 5 × 10-4Pa, process power 8kW, deposition rate 0.16nm/s, and pressure 0.45 Pa. Thus, the preparation of the ITO film is completed.
Here, in order to have a more intuitive feeling of the change of the oxygen/argon ratio during the steps 801 to 802, please refer to fig. 15. FIG. 15 is a graph showing the change of oxygen/argon ratio with respect to the deposition time during steps 801 to 802, wherein the abscissa in FIG. 15 represents the entire deposition time for preparing an ITO thin film and the ordinate in FIG. 15 represents the change of oxygen/argon ratio when preparing an ITO thin film; it should be noted that fig. 15 shows the oxygen/argon ratio in a normalized manner, that is, the oxygen/argon ratio during step 801 (i.e., during the deposition of the first sub-ITO film) is 1, and the oxygen/argon ratios in other steps are all changed with the oxygen/argon ratio during step 801 as a reference.
Fig. 16 is a graph comparing the ITO thin film prepared in this example (i.e., the ITO thin film prepared in accordance with steps 801 to 802 described above) with TTe of the ITO thin film of the related art, in which the solid line represents TTe of the ITO thin film prepared in this example as a function of wavelength, and the dotted line represents TTe of the ITO thin film of the related art as a function of wavelength. As can be seen from FIG. 16, in the near infrared band, TTe of the ITO thin film prepared in this example is significantly improved compared with the ITO thin film in the prior art, especially in the long wavelength band of 1000-1200nm, the average value of TTe is improved by 0.62%. Thus, the optical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
As shown in table 7, which is a comparison table of the ITO thin film prepared in this example and the ITO thin film in the prior art after normalization of the sheet resistance, the carrier concentration, and the carrier mobility, it can be seen from table 7 that, compared with the ITO thin film in the prior art, the sheet resistance of the ITO thin film prepared in this example is reduced by 23%, and both the carrier concentration and the carrier mobility are significantly improved; therefore, the electrical properties of the ITO film prepared in this example are superior to those of the ITO films of the prior art.
TABLE 7
Square resistor Current carryingSub concentration Carrier mobility
ITO film in prior art 1.00 1.00 1.00
ITO film prepared in this example 0.77 1.65 1.83
As shown in table 8, a table comparing the maximum output power Pmax, the photoelectric conversion efficiency Eff, the open circuit voltage Voc, the short circuit current Isc, and the fill factor FF of the HJT cell using the ITO thin film prepared in this example with those of the prior art. As can be seen from table 8, compared with the HJT cell using the ITO thin film of the prior art, the open-circuit voltage Voc, the short-circuit current Isc, and the fill factor FF of the HJT cell using the ITO thin film prepared in this example are all improved, wherein the open-circuit voltage Voc is improved by 0.3%, the short-circuit current Isc is improved by 0.6%, and the fill factor FF is improved by 0.9%, and finally the maximum output power Pmax and the photoelectric conversion efficiency Eff are both improved by 1.8%.
TABLE 8
Figure BDA0001930107130000191
Fig. 17 is a graph comparing the EQE of the HJT cell using the ITO thin film prepared in this example with that of the prior art ITO thin film, in which the solid line shows the change in EQE with wavelength of the HJT cell using the ITO thin film prepared in this example, and the dotted line shows the change in EQE with wavelength of the HJT cell using the prior art ITO thin film. As can be seen from fig. 17, in the near infrared band, the EQE of the ITO thin film prepared in this example is significantly improved compared to the ITO thin film in the prior art, and especially in the band above 1000nm, the EQE improvement amount reaches above 3.3%. Therefore, as can be seen from table 8 and fig. 17, when the ITO thin film prepared in this example is applied to an HJT cell, the performance of the HJT cell can be improved and enhanced in various aspects, and finally, the photoelectric conversion efficiency of the cell is enhanced.
The following is another ITO in TCO film: the Zr thin film is exemplified by:
for example one
For example, in one embodiment of the present invention, the ratio of ITO: the preparation method of the Zr film comprises the following four steps:
step 901, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition for 1 minute according to a first preset condition to obtain a first layer of ITO and ZR film, wherein the first preset condition comprises that the oxygen-argon ratio is 0.98%, and the background vacuum degree is 2 × 10- 4Pa, the process power is 3kW, the deposition rate is 0.15nm/s, and the pressure is 0.4 Pa;
step 902, under the condition of keeping the argon flow unchanged, carrying out physical vapor deposition on the first ITO/ZR thin film for 2 minutes according to a fourth preset condition to obtain a first transition ITO/ZR thin film layer, wherein the fourth preset condition comprises that the oxygen-argon ratio is 1.45%, and the background vacuum degree is 2 × 10-4Pa, process power of 6kW, deposition rate of 0.19nm/s, and pressure of 0.45 Pa;
step 903, under the condition that the flow of the argon gas is kept unchanged, carrying out physical vapor deposition on the first transitional ITO/ZR thin film layer for 2 minutes according to a fifth preset condition to obtain a second transitional ITO/ZR thin film layer, wherein the fifth preset condition comprises that the oxygen-argon ratio is 1.98%, and the background vacuum degree is 2 × 10-4Pa, the process power is 7kW, the deposition rate is 0.2nm/s, and the pressure is 0.45 Pa;
step 904, under the condition that the argon flow is kept unchanged, carrying out physical vapor deposition on the first layer of the sub ITO/ZR film for 2 minutes according to a second preset condition to obtain a second layer of the sub ITO/ZR film, wherein the second preset condition comprises that the oxygen-argon ratio is 2.4 percent, and the background vacuum degree is 2 × 10-4Pa, process power of 7kW, and deposition rate of 0.19nm/s and a pressure of 0.45 Pa. Thus, the ITO is completed: and preparing a ZR film.
Here, in order to have a more intuitive feeling of the change of the oxygen/argon ratio during the steps 901 to 904, please refer to fig. 18. As shown in fig. 18, the oxygen/argon ratio varies with the deposition time during steps 901 to 904, wherein the abscissa in fig. 18 represents the ITO: the overall deposition time of the ZR film, the ordinate in fig. 18 represents the ITO: oxygen to argon ratio change for ZR films; it should be noted that fig. 18 shows the oxygen/argon ratio in a normalized manner, that is, the oxygen/argon ratio during step 901 (i.e., during the deposition of the first layer of ITO: ZR thin film) is 1, and the oxygen/argon ratios in other steps are all changed by taking the oxygen/argon ratio during step 901 as a reference.
Shown in fig. 19 is ITO prepared in this example: the ZR film (i.e., the ITO prepared according to steps 901 to 904: ZR film) is similar to the ITO of the prior art: TTe comparison of ZR films, where the solid line represents the ITO prepared in this example: TTe of the ZR film varies with wavelength, and the dashed line represents the prior art ITO: TTe for the ZR film varies with wavelength. As can be seen from fig. 19, in the near infrared band, the ITO: TTe for ZR film compared to prior art ITO: the ZR film is greatly improved, and particularly in the long wave band of 1000-1200nm, the average value of TTe is improved by 1.26 percent. Thus, the ITO prepared in this example: the optical properties of the ZR films are superior to ITO in the prior art: optical properties of the ZR film.
Table 9 shows the ITO prepared in this example: ZR thin films with ITO in the prior art: the comparison table of the ZR film after the sheet resistance, carrier concentration and carrier mobility normalization is shown in table 9, and compared with the ITO in the prior art: ZR films compared to the ITO prepared in this example: the square resistance of the ZR film is reduced by 25%, and the carrier mobility is improved; thus, the ITO prepared in this example: the electrical properties of the ZR films are superior to ITO in the prior art: a ZR film.
TABLE 9
Figure BDA0001930107130000211
Table 10 shows the ITO prepared in this example: the ZR film HJT battery is compared with the ITO of the prior art: and the maximum output power Pmax, the photoelectric conversion efficiency Eff, the open-circuit voltage Voc, the short-circuit current Isc and the filling factor FF of the HJT battery with the ZR film. As can be seen from Table 10, in comparison with the ITO of the prior art: compared with the HJT battery of the ZR film, the ITO prepared in the example is adopted: the open-circuit voltage Voc, the short-circuit current Isc and the fill factor FF of the HJT cell of the ZR film are all improved to different degrees, wherein the open-circuit voltage Voc is improved by 0.4%, the short-circuit current Isc is improved by 1%, the fill factor FF is improved by 2.5%, and finally the maximum output power Pmax and the photoelectric conversion efficiency Eff are both improved by 3%.
Watch 10
Figure BDA0001930107130000212
FIG. 20 shows the ITO prepared in this example: the ZR film HJT battery is compared with the ITO of the prior art: EQE vs. ZR thin film HJT cell, where the solid line represents the ITO: the EQE of the HJT cell of ZR thin film varies with wavelength, and the dashed line represents ITO: the EQE of the HJT cell of ZR thin film varies with wavelength. As can be seen from fig. 20, the ITO prepared in this example: the EQE of the ZR film is more than that of the ITO in the prior art: the ZR films are all improved, and especially in the wave band above 1000nm, the EQE lifting amount reaches 1.5 percent. Thus, by combining Table 10 and FIG. 20, the ITO prepared in this example: when the ZR film is applied to the HJT battery, the performance of the HJT battery can be improved and promoted from all aspects, and finally the photoelectric conversion efficiency of the battery is promoted.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.

Claims (13)

1. A preparation method of a transparent conductive oxide TCO film is characterized by comprising the following steps:
depositing according to a first preset condition and a first preset time to obtain a first layer of sub TCO film, wherein the first preset condition comprises a first oxygen-argon ratio;
and depositing on the first layer of sub-TCO film according to a second preset condition and a second preset time to obtain a second layer of sub-TCO film, wherein the second preset condition comprises a second oxygen-argon ratio which is greater than the first oxygen-argon ratio.
2. The method for preparing a TCO film according to claim 1, wherein the first sub-TCO film is an indium tin oxide ITO film and a zirconium-doped indium tin oxide ITO: any one of Zr films, the second layer of sub-TCO film is an ITO film and ITO: any one of Zr thin films;
when the first layer of sub-TCO film and the second layer of sub-TCO film are both ITO films, the first oxygen-argon ratio is greater than or equal to 1% and less than 3%, and the second oxygen-argon ratio is greater than or equal to 7% and less than 9%;
when the first layer of sub-TCO film and the second layer of sub-TCO film are both ITO: in the case of the Zr thin film, the first oxygen-argon ratio is more than or equal to 0.5% and less than 1%, and the second oxygen-argon ratio is more than or equal to 2% and less than 2.5%.
3. The method for preparing TCO film according to claim 1 or 2, wherein the first predetermined condition further comprises that the background vacuum degree reaches at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the first preset time is more than 0 and less than or equal to 5 minutes;
the second preset condition further comprises that the background vacuum degree reaches at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the second preset time is greater than 0 and less than or equal to 5 minutes.
4. The method for producing a TCO film according to claim 1, further comprising:
depositing on the first layer of sub-TCO film according to a third preset condition and a third preset time before the step of obtaining the second layer of sub-TCO film to obtain a third layer of sub-TCO film, wherein the third preset condition comprises a third oxygen-argon ratio which is greater than the first oxygen-argon ratio and less than the second oxygen-argon ratio;
and depositing on the third layer of sub-TCO film according to the second preset condition and the second preset time after the step of obtaining the third layer of sub-TCO film to form the second layer of sub-TCO film.
5. The method for preparing the TCO film according to claim 4, wherein the third sub-TCO film is an ITO film and an ITO: any one of Zr thin films;
when the third layer of sub-TCO film is an ITO film, the third oxygen-argon ratio is greater than or equal to 3% and less than 7%;
when the third layer of sub-TCO film is ITO: in the case of the Zr thin film, the third oxygen-argon ratio is more than or equal to 1% and less than 2%.
6. The method for preparing TCO film according to claim 4 or 5, wherein the third predetermined condition further comprises that the background vacuum degree reaches at least 9 × 10-4Pa, the range of the process power is more than 0 and less than 15kW, the range of the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the third predetermined time is greater than or equal to 1.5 minutes and less than or equal to 3 minutes.
7. The method for producing a TCO film according to claim 4, further comprising:
depositing on the first layer of sub TCO film according to a fourth preset condition and a fourth preset time to obtain a first layer of transition TCO film, wherein the fourth preset condition comprises a fourth oxygen-argon ratio which is greater than the first oxygen-argon ratio;
depositing on the first transition TCO thin film layer according to a fifth preset condition and according to a fifth preset time to obtain a second transition TCO thin film layer, wherein the fifth preset condition comprises a fifth oxygen-argon ratio which is larger than the fourth oxygen-argon ratio and smaller than the second oxygen-argon ratio;
forming the third sub-TCO film from the first transition TCO film layer and the second TCO film layer;
and after the step of obtaining the second transitional TCO film layer, depositing on the second transitional TCO film layer according to the second preset condition and the second preset time to form the second sub-TCO film layer.
8. The method for preparing the TCO film according to claim 7, wherein the first transition TCO film layer is an ITO film layer and an ITO: any one of the Zr thin film layers, the second transition TCO thin film layer is an ITO thin film layer and ITO: any one of the Zr thin film layers;
when the first transition TCO thin film layer and the second transition TCO thin film layer are ITO thin film layers, the fourth oxygen-argon ratio is greater than or equal to 3% and less than 5%, and the fifth oxygen-argon ratio is greater than or equal to 5% and less than 7%;
when the first transition TCO thin film layer and the second transition TCO thin film layer are both ITO: in the case of the Zr thin film layer, the fourth oxygen/argon ratio is 1% or more and less than 1.5%, and the fifth oxygen/argon ratio is 1.5% or more and less than 2%.
9. The method for preparing a TCO film according to claim 7 or 8, wherein the fourth predetermined condition further comprises:background vacuum of at least 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the range of the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the fourth preset time is greater than or equal to 0.5 minutes and less than or equal to 2 minutes;
the fifth preset condition further comprises that the background vacuum degree at least reaches 9 × 10-4Pa, the range of the process power is more than 0 and less than 15kW, the range of the deposition rate is more than 0 and less than 1.5nm/s, and the range of the pressure intensity is more than or equal to 0.2Pa and less than 0.8 Pa;
the fifth predetermined time is greater than or equal to 0.5 minutes and less than or equal to 2 minutes.
10. The method for producing a TCO film according to claim 4, further comprising:
before the step of obtaining the first layer of sub-TCO film, depositing according to a sixth preset condition and a sixth preset time to obtain a fourth layer of sub-TCO film, wherein the sixth preset condition comprises a sixth oxygen-argon ratio which is more than 0 and less than the first oxygen-argon ratio;
and depositing on the fourth layer of sub-TCO film according to the first preset condition and the first preset time after the step of obtaining the fourth layer of sub-TCO film to form the first layer of sub-TCO film.
11. The method for preparing the TCO film according to claim 10, wherein the fourth sub-TCO film is an ITO film and an ITO: any one of Zr thin films;
when the fourth sub-TCO film is an ITO film, the sixth oxygen-argon ratio is greater than 0 and less than 1%;
when the fourth sub-TCO film is ITO: in the case of the Zr thin film, the sixth oxygen-argon ratio is more than 0 and less than 0.5%.
12. The method for preparing a TCO film according to claim 10,characterized in that the sixth preset condition also comprises that the background vacuum degree at least reaches 9 × 10-4Pa, the process power is more than 0 and less than 15kW, the deposition rate is more than 0 and less than 1.5nm/s, and the pressure is more than or equal to 0.2Pa and less than 0.8 Pa;
the sixth predetermined time is greater than or equal to 0.5 minutes and less than or equal to 2 minutes.
13. The method of producing a TCO film according to claim 10, wherein the first, second, third and fourth TCO films are deposited with the same flow of argon gas.
CN201811636224.6A 2018-12-29 2018-12-29 Method for preparing transparent conductive oxide film Pending CN111446149A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112701194A (en) * 2020-12-29 2021-04-23 晋能清洁能源科技股份公司 Preparation method of heterojunction solar cell

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112701194A (en) * 2020-12-29 2021-04-23 晋能清洁能源科技股份公司 Preparation method of heterojunction solar cell

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