CN112331729A - Light absorbing layer of CIGS thin film solar cell and method for forming the same - Google Patents
Light absorbing layer of CIGS thin film solar cell and method for forming the same Download PDFInfo
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- H10F77/10—Semiconductor bodies
- H10F77/12—Active materials
- H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
- H10F77/1265—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS] characterised by the dopants
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- H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
- H10F10/14—Photovoltaic cells having only PN homojunction potential barriers
- H10F10/146—Back-junction photovoltaic cells, e.g. having interdigitated base-emitter regions on the back side
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Abstract
本发明涉及太阳能电池技术领域，具体涉及一种CIGS薄膜太阳能电池的光吸收层及其形成方法；所述光吸收层的预制结构包括依次连接的玻璃衬底、背电极、吸收中层、Se层，所述吸收中层包括自背电极向Se层方向依次沉积的Cu‑Na合金层、Cu‑Ga合金层和In层。本发明具有下述有益技术效果：本发明在光吸收层中镀膜多层Na元素，在热处理下，Na元素在光吸收层中有效迁移，因此实现光吸收层中Na含量的精准控制和均匀分布，通过多层Na元素掺杂，促进CIGS吸收层结晶，优化Ga元素在吸收层中的分布。The invention relates to the technical field of solar cells, in particular to a light absorption layer of a CIGS thin film solar cell and a method for forming the same; the prefabricated structure of the light absorption layer comprises a glass substrate, a back electrode, an absorption middle layer, and an Se layer that are connected in sequence, The absorption middle layer includes a Cu-Na alloy layer, a Cu-Ga alloy layer and an In layer sequentially deposited from the back electrode toward the Se layer. The present invention has the following beneficial technical effects: the present invention coats a multi-layer Na element in the light absorbing layer, and under heat treatment, the Na element migrates effectively in the light absorbing layer, thus realizing precise control and uniform distribution of the Na content in the light absorbing layer , Through the multi-layer Na element doping, the crystallization of the CIGS absorber layer is promoted, and the distribution of Ga element in the absorber layer is optimized.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a light absorption layer of a CIGS thin-film solar cell and a forming method thereof.
Background
Thin film solar cells, such as amorphous silicon solar cells and compound thin film solar cells, can significantly reduce material costs and manufacturing costs compared to conventional crystalline silicon solar cells, and are one of the important fields of research and development in recent years. Among them, compound thin-film solar cells using elements of groups i, iii, and vi as constituent materials, particularly CIGS solar cells using a CIGS film formed of an alloy of copper (Cu), indium (In), gallium (Ga), and selenium (Se) as a light absorbing layer have attracted attention because they do not use silicon at all and have excellent solar light conversion efficiency.
The light absorbing layer is the core of the CIGS solar cell. Research shows that trace Na doping can promote crystallization of the light absorption layer, optimize electrical performance of the CIGS solar cell and improve conversion efficiency and yield. Research on a Na element doping technology with active properties is one of important directions for improving the efficiency of a CIGS solar cell. In the prior art, a doping method for transferring Na in a soda-lime glass substrate to a light absorption layer by using heat treatment cannot ensure the distribution uniformity of Na elements in the light absorption layer, and a Na element doping technology with more stability, uniformity and controllability still needs to be further researched.
Disclosure of Invention
The primary object of the present invention is to provide a prefabricated structure of a CIGS thin-film solar cell light absorption layer to achieve uniform distribution of Na elements in the light absorption layer.
A prefabricated structure of a light absorption layer of a CIGS thin-film solar cell comprises a glass substrate, a back electrode, an absorption middle layer and an Se layer which are sequentially connected, wherein the absorption middle layer comprises a Cu-Na alloy layer, a Cu-Ga alloy layer and an In layer which are sequentially deposited from the back electrode to the Se layer.
In a preferred embodiment of the present invention, the glass substrate is selected from any one of soda lime glass, medium alumina glass, and high alumina glass.
The preferable scheme of the invention is that the back electrode comprises two double-layer Mo films and an SiN layer positioned between the two double-layer Mo films, the thickness of the back electrode is 100-500nm, and the thickness of the SiN layer is 10-200 nm.
In a preferred embodiment of the present invention, at least 2 absorbing intermediate layers are included between the back electrode and the Se layer.
Another object of the present invention is to provide a method for forming a prefabricated structure of a light absorbing layer of a CIGS thin-film solar cell as described above, comprising the steps of:
s1: depositing a Mo film, a SiN layer and a Mo film on a glass substrate in sequence by adopting magnetron sputtering to form a back electrode;
s2: depositing a Cu-Na alloy layer, a Cu-Ga alloy layer and an In layer on the back electrode In sequence by adopting magnetron sputtering to form an absorption middle layer;
s3: forming a Se layer by sputtering Se vapor onto the absorbing middle layer by a sputtering method;
the number of operations of step S2 is at least 2.
The preferred scheme of the invention is that the magnetron sputtering method comprises the following steps: evacuating the operating cavity to (0.5-2) × 10- 6mbar, carrying out sputtering on the Mo target material or the SiN target material or the CuNa target material or the CuGa target material or the In target material, wherein the sputtering temperature is 20-30 ℃, the sputtering power is 3-8kW, the Ar flow is 400-plus-10 sccm, and the sputtering pressure is (2-4) × 10-3mbar。
In a preferred embodiment of the present invention, in the absorption intermediate layer, the Na content in the Cu-Na alloy layer is 30 to 150ng/cm2。
In a preferable embodiment of the present invention, in the absorbing intermediate layer, the Cu content in the Cu-Ga alloy layer is 30 to 140 μ g/cm2。
In a preferred embodiment of the present invention, in the absorbing intermediate layer, the Ga content in the Cu-Ga alloy layer is 10 to 60 μ g/cm2。
In the preferable scheme of the invention, In content In the In layer In the absorption intermediate layer is 40-180 mug/cm2。
The preferable scheme of the invention is that the Se content in the Se layer is 550-2。
A further object of the present invention is to provide a method for forming a CIGS thin-film solar cell light absorbing layer, comprising heat-treating the prefabricated structure as described above or the prefabricated structure formed by any one of the above methods to obtain a CIGS thin-film solar cell light absorbing layer; the heat treatment temperature is 400-650 ℃, and the heat treatment time is 5-30 minutes.
It is still another object of the present invention to provide a CIGS thin-film solar cell light absorbing layer formed by the above method.
It is a further object of the present invention to provide a CIGS thin-film solar cell including a CIGS thin-film solar cell light absorbing layer formed according to the method as described above or a CIGS thin-film solar cell light absorbing layer as described above.
Unless otherwise indicated, when the present invention relates to percentages between liquids, said percentages are volume/volume percentages; the invention relates to the percentage between liquid and solid, said percentage being volume/weight percentage; the invention relates to the percentages between solid and liquid, said percentages being weight/volume percentages; the balance being weight/weight percent.
Compared with the prior art, the invention has the following beneficial technical effects: according to the invention, the Na element is coated in the light absorption layer, and under the heat treatment, the Na element effectively migrates in the light absorption layer, so that the accurate control and uniform distribution of the Na content in the light absorption layer are realized.
Drawings
Fig. 1 is a schematic structural view of example 1 of the present invention (the number of layers of the absorbing layer 30 is 2);
FIG. 2 is a schematic diagram of a technical implementation process of embodiment 5 of the present invention;
fig. 3 is a schematic diagram of a technical implementation process of embodiment 6 of the present invention.
Detailed Description
The present invention will be described below with reference to examples, but the present invention is not limited to the examples.
Example 1 prefabricated Structure of light absorbing layer of CIGS thin-film solar cell
Referring to fig. 1, a prefabricated structure of a light absorbing layer of a CIGS thin-film solar cell includes a glass substrate 10, a back electrode 20, an absorbing intermediate layer 30, and a Se layer 40, which are sequentially connected.
The glass substrate 10 is soda-lime glass.
The back electrode 20 comprises two double-layer Mo films 21 and an SiN layer 22 located between the two double-layer Mo films 21, the thickness of the back electrode 20 is 400nm, the thickness of the SiN layer 22 is 50nm, and the thicknesses of the upper Mo film 21 and the lower Mo film 21 are respectively 200nm and 150 nm.
The absorption intermediate layer 30 includes a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32, and an In layer 33 sequentially deposited from the back electrode 20 toward the Se layer 40;
the number of layers of the absorbing middle layer 30 is 2.
In the absorbing middle layer 30, the Cu content in the Cu-Na alloy layer 31 is 7 mug/cm2Na content of 280ng/cm2(ii) a The total Cu content in the Cu-Ga alloy layer 32 is 170 [ mu ] g/cm2The total content of Ga is 50 mu g/cm2(ii) a The total In content In the In layer 33 was 220. mu.g/cm2。
The total content of Se in the Se layer 40 is 600 mu g/cm2。
Example 2 method for Forming prefabricated Structure of light absorbing layer of CIGS thin film solar cell
A method for forming a prefabricated structure of a CIGS thin-film solar cell light absorption layer comprises the following steps:
s1: respectively taking a metal Mo target and a metal SiN target as targets, and sequentially depositing a Mo film 21, a SiN layer 22 and the Mo film 21 on the glass substrate 10 by adopting magnetron sputtering to form a back electrode 20;
s2: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the back electrode 20 by magnetron sputtering to form a first absorption middle layer 30;
s3: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the first absorption middle layer 30 by magnetron sputtering to form a second absorption middle layer 30;
s4: se vapor is formed by heating the Se source to a temperature of 800 ℃ or higher, and the Se layer 40 is formed by sputtering Se vapor onto the second absorbing intermediate layer 30 by a sputtering method.
In the above step, the magnetron sputtering method comprises: evacuating the operating cavity of the magnetron sputtering system to 1 x 10- 6mbar, carrying out sputtering on a Mo target material, a SiN target material, a CuNa target material, a CuGa target material or an In target material, wherein the sputtering power is 8kW, the Ar flow is introduced into the target material at 400sccm, and the sputtering pressure is 3 x 10-3mbar。
The thickness of the back electrode 20 is 400nm, the thickness of the SiN layer 22 is 50nm, and the thicknesses of the upper Mo film 21 and the lower Mo film 21 are respectively 200nm and 150 nm.
The Cu content in the total Cu-Na alloy layer 31 in the first absorbing intermediate layer 30 and the second absorbing intermediate layer 30 is 7 [ mu ] g/cm2Na content of 280ng/cm2(ii) a The total Cu content in the total Cu-Ga alloy layer 32 is 170 [ mu ] g/cm2The total content of Ga is 50 mu g/cm2(ii) a The total In content In the total In layer 33 was 220. mu.g/cm2。
The total content of Se in the Se layer 40 is 600 mu g/cm2。
Example 3 method for Forming prefabricated Structure of light absorbing layer of CIGS thin film solar cell
A method for forming a prefabricated structure of a CIGS thin-film solar cell light absorption layer comprises the following steps:
s1: respectively taking a metal Mo target and a metal SiN target as targets, and sequentially depositing a Mo film 21, a SiN layer 22 and the Mo film 21 on the glass substrate 10 by adopting magnetron sputtering to form a back electrode 20;
s2: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the back electrode 20 by magnetron sputtering to form a first absorption middle layer 30;
s3: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the first absorption middle layer 30 by magnetron sputtering to form a second absorption middle layer 30;
s4: se vapor is formed by heating the Se source to a temperature of 800 ℃ or higher, and the Se layer 40 is formed by sputtering Se vapor onto the second absorbing intermediate layer 30 by a sputtering method.
In the above step, the magnetron sputtering method comprises: evacuating the operating cavity of the magnetron sputtering system to 1.8 x 10-6mbar for Mo target, SiN target, CuNa target or CuGa targetSputtering the target material or the In target material, wherein the sputtering power is 9kW, the Ar flow is 400sccm, and the sputtering pressure is 3.8 x 10-3mbar。
The thickness of the back electrode 20 is 418nm, the thickness of the SiN layer 22 is 48nm, and the thicknesses of the upper Mo film 21 and the lower Mo film 21 are respectively 200nm and 170 nm.
The Cu content in the total Cu-Na alloy layer 31 in the first absorbing intermediate layer 30 and the second absorbing intermediate layer 30 is 7 [ mu ] g/cm2Na content of 310ng/cm2(ii) a The total Cu content in the total Cu-Ga alloy layer 32 is 165. mu.g/cm2The total content of Ga is 50 mu g/cm2(ii) a The total In content In the total In layer 33 was 215. mu.g/cm2。
The total content of Se in the Se layer 40 is 615 mu g/cm2。
Example 4 method for Forming prefabricated Structure of light absorbing layer of CIGS thin film solar cell
A method for forming a prefabricated structure of a CIGS thin-film solar cell light absorption layer comprises the following steps:
s1: respectively taking a metal Mo target and a metal SiN target as targets, and sequentially depositing a Mo film 21, a SiN layer 22 and the Mo film 21 on the glass substrate 10 by adopting magnetron sputtering to form a back electrode 20;
s2: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the back electrode 20 by magnetron sputtering to form a first absorption middle layer 30;
s3: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the first absorption middle layer 30 by magnetron sputtering to form a second absorption middle layer 30;
s4: respectively taking a metal CuNa target, a CuGa target and an In target as target materials, and sequentially depositing a Cu-Na alloy layer 31, a Cu-Ga alloy layer 32 and an In layer 33 on the second absorption middle layer 30 by magnetron sputtering to form a third absorption middle layer 30;
s5: se vapor is formed by heating the Se source to a temperature of 800 ℃ or higher, and the Se layer 40 is formed by sputtering Se vapor onto the third absorbing intermediate layer 30 by a sputtering method.
In the above step, the magnetron sputtering method comprises: evacuating the operating cavity of the magnetron sputtering system to 2 x 10- 6mbar, carrying out sputtering on Mo target material, SiN target material, CuNa target material, CuGa target material or In target material, wherein the sputtering power is 8.5kW, the Ar flow is introduced into the target material at 400sccm, and the sputtering pressure is 3.2 x 10-3mbar。
The thickness of the back electrode 20 is 500nm, the thickness of the SiN layer 22 is 60nm, and the thicknesses of the upper Mo film 21 and the lower Mo film 21 are 250nm and 190nm respectively.
The Cu content in the total Cu-Na alloy layer 31 of the first, second and third absorbing middle layers 30, 30 is 7.5 [ mu ] g/cm2Na content of 320ng/cm2(ii) a The total Cu content in the total Cu-Ga alloy layer 32 is 175 μ g/cm2The total content of Ga is 55 mu g/cm2(ii) a The total In content In the total In layer 33 was 230. mu.g/cm2。
The total content of Se in the Se layer 40 is 680 mu g/cm2。
Example 5 method for forming CIGS thin film solar cell light absorbing layer
A prefabricated structure formed in the embodiment 2 is placed in a 570 ℃ temperature environment to be subjected to heat treatment for 10 minutes, and the CIGS thin-film solar cell light absorption layer is obtained.
Example 6 method for forming CIGS thin film solar cell light absorbing layer
A prefabricated structure formed in the embodiment 3 is placed in a temperature environment of 580 ℃ for heat treatment for 10 minutes to obtain the CIGS thin-film solar cell light absorbing layer.
Example 7 method for forming CIGS thin film solar cell light absorbing layer
A prefabricated structure formed in the embodiment 4 is placed in an environment with the temperature of 565 ℃ for heat treatment for 10 minutes to obtain the CIGS thin-film solar cell light absorbing layer.
Performance test
Based on the light-absorbing layers obtained in examples 5, 6, and 7, solar cell modules A, B and C were obtained, and parameters such as Power (module Power), Voc (open circuit voltage), Isc (short circuit current), Rs (series resistance), Rsh (parallel resistance), and the like of the solar cell modules A, B and C were measured at 25 ℃ and 60% humidity using a Halm Power tester to evaluate photoelectric conversion efficiency of the products. The results are shown in table 1 below.
TABLE 1
Claims (10)
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Application publication date: 20210205 |