CN113571594B - Copper indium gallium selenium battery and manufacturing method thereof - Google Patents

Copper indium gallium selenium battery and manufacturing method thereof Download PDF

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CN113571594B
CN113571594B CN202110805785.XA CN202110805785A CN113571594B CN 113571594 B CN113571594 B CN 113571594B CN 202110805785 A CN202110805785 A CN 202110805785A CN 113571594 B CN113571594 B CN 113571594B
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cigs
indium gallium
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CN113571594A (en
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刘武
宋丹丹
朱成皖
李昊天
赵谡玲
乔泊
徐征
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Beijing Jiaotong University
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Abstract

The invention provides a copper indium gallium selenide battery and a manufacturing method thereof, comprising a Copper Indium Gallium Selenide (CIGS) film, wherein the Ga gradient of the CIGS film comprises two minimum values from the front surface close to the buffer layer side to the rear surface close to the back electrode side, and the GGI value and the band gap gradient of the CIGS film are distributed in a W shape. Effectively improve the open circuit voltage V OC Improving the carrier collection efficiency and the short-circuit current J SC Meanwhile, the "W" type gradient contains two regions of low GGI, increasing the absorption probability of long wavelength photons.

Description

Copper indium gallium selenium battery and manufacturing method thereof
Technical Field
The invention relates to the technical field of solar cells, in particular to a copper indium gallium selenide cell and a manufacturing method thereof.
Background
In the process of depositing the copper indium gallium selenide film by the co-evaporation method, the uniformity of the film material, the crystallization structure and other properties are related to the evaporation rate of the constituent elements. Different kinds of gradient distribution are realized, and the longitudinal distribution of Ga content in the film can be controlled by changing the evaporation rate of Ga element by changing the evaporation temperature of a Ga source under the condition that the rest evaporation conditions are the same. In copper indium gallium selenide solar cells, the deep bandgap change due to the change In Ga content (GGI, i.e., ga/(ga+in)) ratio is commonly referred to as a Ga gradient. The absorption band gap of the CIGS film can change along with the ratio of Ga content to form a band gap gradient according to a fixed proportion, and the change of the Ga gradient in the film can bring about the change of the band gap gradient. The GGI gradient distribution types are currently mainly divided into three types, namely a flat gradient, a single gradient and a V-shaped double gradient.
Fig. 1 shows three bandgap curves for copper indium gallium diselenide (CIGS) cells. Wherein (a) represents a flat gradient bandgap profile, the drift of photo-generated electrons generated in other regions than the electrons generated in or near the depletion layer is relatively limited because of the zero gradient of the potential. In contrast, as shown in (b), (c) is the case where a band gap gradient exists, photoelectrons can easily reach the depletion region, thereby improving carrier collection efficiency. Currently, copper indium gallium diselenide solar cells with a V-shaped dual-gradient band gap structure as shown in (c) achieve the highest efficiency: the increase of the band gap of the surface and the back surface inhibits the recombination of the battery absorption area, effectively improves the open circuit voltage V OC The method comprises the steps of carrying out a first treatment on the surface of the The middle narrow band gap can reduce the spectral response loss of the battery in a long wave band, thereby enabling the short-circuit current J SC The loss of (2) is minimized.
In the optimization process of the band gap gradient distribution of the copper indium gallium selenide battery from a flat band gap to a single band gap to a V-shaped double band gap, the gain optimization of the battery performance is always improved. However, in the prior art, compared with the efficiency limit of the Shockley-Queisser (S-Q), the loss of the open-circuit voltage of the copper indium gallium selenide battery still reaches more than 350mV, the short-circuit current loss is the largest in the third generation thin film solar battery, and reaches more than 10%, so that the battery performance is still greatly improved.
Disclosure of Invention
The invention provides a copper indium gallium selenium battery and a manufacturing method thereof, which are used for solving the defects existing in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A CIGS cell comprises a CIGS film, wherein the Ga gradient of the CIGS film comprises two minima from the front surface close to the buffer layer side to the rear surface close to the back electrode side, and the GGI value and the band gap gradient of the CIGS film both show W-shaped distribution.
Preferably, the cell includes a substrate, a back electrode, a CIGS thin film, a buffer layer, an electron transport layer, and a transparent front electrode.
Preferably, the front surface GGI value of the CIGS film is 0.25-0.65, and the band gap of the front surface of the CIGS film and the conduction band mismatch value CBO of the n-type buffer layer of the CIGS cell are kept at-0.05-0.1 eV.
Preferably, the band gap gradient has a GGI minimum of 0.1 to 0.5.
Preferably, the CIGS thin film has a rear surface GGI value of 0.5 to 1.
Another aspect of the present invention provides a method for manufacturing the copper indium gallium selenide battery, including:
preparing a molybdenum electrode layer with the thickness of 100-1000 nanometers on a battery substrate by adopting a direct current magnetron sputtering method;
depositing a CIGS film with the thickness of 0.5-5 micrometers on the molybdenum electrode layer by adopting a three-step co-evaporation method; GGI is regulated and controlled by controlling evaporation rates of Ga and In sources at different stages, so that the band gap of CIGS is regulated, and W-shaped band gap gradient distribution is formed;
alkali post-treatment of CIGS with NaF, KF, rbF or CsF alkali source materials;
depositing an n-type film with the thickness of 10-100 nanometers on the CIGS layer subjected to alkali metal post treatment by adopting a chemical bath deposition method as a buffer layer;
preparing a zinc oxide layer with the thickness of 50-500 nanometers on the buffer layer by adopting a direct current magnetron sputtering method as an electron transmission layer;
and preparing an AZO layer with the thickness of 150-1000 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method to serve as a transparent front electrode.
Preferably, AZO is aluminum-doped zinc oxide.
As can be seen from the technical solution provided by the above-mentioned copper indium gallium selenide battery and the manufacturing method thereof, the invention optimizes the gradient distribution of band gap in order to solve the problem of device performance loss in the existing copper indium gallium selenide battery, and under the condition that the total content of Ga in the CIGS thin film is the same, by setting the distribution of GGI value in the CIGS thin film from the front surface close to the buffer layer side to the rear surface close to the back electrode side, the Ga gradient comprises two minimum values, and the CIGS thin filmThe GGI and band gap gradients of the film show W-shaped distribution, so that the GGI value of the front surface and GGI value of the rear surface of the CIGS film are higher, the wide band gap of the W-shaped gradient on the surface and the back of the CIGS film inhibits the recombination of the absorption area of the cell, and the open-circuit voltage V is effectively improved OC The method comprises the steps of carrying out a first treatment on the surface of the The increase of GGI value on the rear surface forms a high back electric field, improves the carrier collection efficiency and improves the short-circuit current J SC And open circuit voltage V OC Meanwhile, the "W" type gradient contains two regions of low GGI, increasing the absorption probability of long wavelength photons.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of three bandgap curves of a copper indium gallium diselenide (CIGS) cell;
fig. 2 is a schematic diagram of a CIGS thin film bandgap gradient design for a copper indium gallium diselenide cell according to an embodiment;
fig. 3 is a flowchart of a method for manufacturing a copper indium gallium selenide battery according to an embodiment.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary only for explaining the present invention and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless expressly stated otherwise, as understood by those skilled in the art. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It is to be understood that "connected" or "coupled" as used herein may include wireless connections or couplings. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For the purpose of facilitating an understanding of the embodiments of the present invention, reference will now be made to the drawings, by way of example, and not to the limitation of the embodiments of the present invention.
Examples
The embodiment provides a Copper Indium Gallium Selenide (CIGS) battery, which comprises a Copper Indium Gallium Selenide (CIGS) film, fig. 2 is a schematic diagram of band gap gradient design of the CIGS film of the Copper Indium Gallium Selenide (CIGS) battery, and referring to fig. 2, the Ga gradient of the CIGS film comprises two minimum values from the front surface close to the buffer layer side to the rear surface close to the back electrode side, and the GGI value and the band gap gradient of the CIGS film are distributed in a W shape. GGI is Ga content, ggi=ga/(ga+in).
The cell of this embodiment includes a substrate, a back electrode, a CIGS thin film, a buffer layer, an electron transport layer, and a transparent front electrode.
The GGI value of the front surface of the CIGS film is 0.25-0.65, and the band gap of the front surface of the CIGS film and the conduction band mismatch value CBO of the n-type buffer layer of the CIGS cell are kept at-0.05-0.1 eV is provided. It should be noted that the design of the CIGS cell band gap gradient is applicable to different n-type buffer layers, including CdS, zn (O, S) and In 2 S 3 、ZnS、Zn 1-x Mg x O, the gain of which is common.
The GGI minimum value of the band gap gradient is 0.1-0.5, and the GGI value of the back surface of the CIGS film is 0.5-1.
Another aspect of the present embodiment provides a method for manufacturing a copper indium gallium selenide battery, fig. 3 is a flowchart of a method for manufacturing a copper indium gallium selenide battery, and referring to fig. 3, the method includes the following steps:
s101: and preparing a molybdenum electrode layer with the thickness of 500 nanometers on the battery substrate by adopting a direct current magnetron sputtering method.
The battery substrate of this example was 3mm glass.
S102: and a W-shaped band gap gradient copper indium gallium selenium film with the thickness of 1 micron is deposited on the molybdenum electrode layer by adopting a three-step co-evaporation method.
The GGI duty ratio is regulated and controlled by controlling the evaporation rates of Ga and In sources In different stages, so that the band gap of CIGS is regulated, and W-shaped band gap gradient distribution is formed.
Specifically, the deposition process needs to deposit In, ga and Se In a sufficient Se atmosphere environment In an evaporation way at a lower substrate temperature (260-400 ℃) to form a compound prefabricated layer consisting of the In, ga and Se; second, turning off In source and Ga source, turning on Cu source at higher substrate temperature (550-600 deg.C) to obtain copper-rich CIGS layer, at high temperature, copper is used as Cu 2-x The liquid form of the Se secondary phase; finally, evaporating In and Ga sources and Cu under the condition that the substrate is still at high temperature 2-x Se reacts to finally form a CIGS film with a thickness of 1 micrometer.
The step provides a high-efficiency W-shaped Ga gradient distribution value, wherein the total GGI value is 0.58, the GGI value of the front surface of the CIGS film is 0.51-0.62, the minimum GGI value of the first GGI value is 0.49-0.51, the middle GGI value is 0.51-0.62, the minimum GGI value of the second GGI value is 0.49-0.51, and the GGI value of the rear surface of the CIGS film is 0.74-0.96.
S103: and (3) evaporating CsF of 5 nanometers on the top of the copper indium gallium selenide film by adopting thermal evaporation to carry out alkali metal post-treatment, and then carrying out annealing treatment.
Diffusing an alkali metal element to the surface or the inside of the CIGS thin film through a post-annealing process at 350 ℃;
and S104, adopting a Chemical Bath Deposition (CBD) method to deposit cadmium sulfide with the thickness of 50 nanometers on the CIGS film subjected to alkali metal post-treatment as a buffer layer.
S105, preparing a zinc oxide layer with the thickness of 100 nanometers on the buffer layer by adopting a direct current magnetron sputtering method. The zinc oxide layer is an electron transport layer, the electron transport layer adopts zinc oxide, and a zinc oxide layer with the thickness of 100 nanometers is prepared on the perovskite layer by adopting a magnetron sputtering method.
S106: and preparing an AZO layer with the thickness of 200 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method to serve as a transparent front electrode.
In the step, the transparent front electrode adopts AZO which is aluminum-doped zinc oxide, and an AZO layer with the thickness of 200 nanometers is prepared on the electron transport layer by adopting a magnetron sputtering method.
In summary, the CIGS cell and the manufacturing method thereof provided in the embodiment inhibit the recombination of the absorption region of the cell by increasing the band gap of the front surface of the CIGS thin film, thereby effectively increasing the open circuit voltage V OC The method comprises the steps of carrying out a first treatment on the surface of the The high back electric field is formed by utilizing the increase of the band gap of the back surface of the CIGS film, the carrier collection efficiency is improved, and the short-circuit current J is improved SC And open circuit voltage V OC The method comprises the steps of carrying out a first treatment on the surface of the The use of two low GGI regions reduces the spectral response loss of the cell in the long wavelength band while increasing the absorption probability of long wavelength photons. It enables copper indium gallium selenide solar cells to achieve higher than 23.35% photoelectric conversion efficiency relative to the highest efficiency achieved by the current "V" type double gradient.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims (7)

1. The CIGS thin film comprises a front surface close to a buffer layer side and a rear surface close to a back electrode side, wherein the Ga gradient comprises two minima, and the GGI value and the band gap gradient of the CIGS thin film are distributed in a W shape; GGI is Ga content, ggi=ga/(ga+in);
in the W-type Ga gradient distribution value, the GGI value of the front surface of the CIGS thin film is 0.51-0.65, and the GGI value of the rear surface of the CIGS thin film is 0.74-1.
2. The copper indium gallium selenide cell of claim 1, wherein the cell comprises a substrate, a back electrode, a CIGS thin film, a buffer layer, an electron transport layer, and a transparent front electrode.
3. The copper indium gallium selenide cell according to claim 1, wherein the front surface GGI value of the CIGS thin film is 0.51 to 0.62, and the front surface band gap of the CIGS thin film and the conduction band mismatch value CBO of the n-type buffer layer of the copper indium gallium selenide cell are maintained at-0.05 to 0.1eV.
4. The copper indium gallium selenide cell according to claim 1, wherein the GGI minimum value of the band gap gradient is 0.1 to 0.5.
5. The copper indium gallium selenide cell of claim 1, wherein the CIGS thin film has a GGI value of 0.74 to 0.96 on the back surface.
6. A method of manufacturing a copper indium gallium diselenide battery according to any one of claims 1 to 5, comprising:
preparing a molybdenum electrode layer with the thickness of 100-1000 nanometers on a battery substrate by adopting a direct current magnetron sputtering method;
depositing a CIGS film with the thickness of 0.5-5 micrometers on the molybdenum electrode layer by adopting a three-step co-evaporation method; GGI is regulated and controlled by controlling evaporation rates of Ga and In sources In different stages, so that the band gap of CIGS is regulated, and W-shaped band gap gradient distribution is formed;
alkali post-treatment of CIGS with NaF, KF, rbF or CsF alkali source materials;
depositing an n-type film with the thickness of 10-100 nanometers on the CIGS layer subjected to the alkali metal post treatment by adopting a chemical bath deposition method as a buffer layer;
preparing a zinc oxide layer with the thickness of 50-500 nanometers on the buffer layer by adopting a direct current magnetron sputtering method as an electron transmission layer;
and preparing an AZO layer with the thickness of 150-1000 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method to serve as a transparent front electrode.
7. The method of claim 6, wherein AZO is aluminum-doped zinc oxide.
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