CN111755538B - Preparation method of copper zinc tin germanium selenium absorption layer film with germanium gradient - Google Patents

Preparation method of copper zinc tin germanium selenium absorption layer film with germanium gradient Download PDF

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CN111755538B
CN111755538B CN202010592249.1A CN202010592249A CN111755538B CN 111755538 B CN111755538 B CN 111755538B CN 202010592249 A CN202010592249 A CN 202010592249A CN 111755538 B CN111755538 B CN 111755538B
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CN111755538A (en
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王书荣
杨帅
徐信
李新毓
李祥
王亭保
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Yunnan Normal University
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Abstract

The invention discloses a preparation method of a copper zinc tin germanium selenium absorption layer film with a germanium gradient, which specifically comprises the following steps: (1) substrate pretreatment; (2) preparation of molybdenum layer and germanium layer: sequentially depositing a first molybdenum layer, a germanium layer and a second molybdenum layer on the pretreated substrate; (3) preparing a copper zinc tin sulfide prefabricated layer; (4) preparation of a copper zinc tin germanium selenium absorption layer film: carrying out heat treatment on the substrate after the preparation of the copper zinc tin sulfur prefabricated layer in the step (3) at 210 ℃ for 30min, then placing the substrate and selenium powder into a selenizing furnace, heating from room temperature to 550 ℃ at a heating rate of 20 ℃/min, preserving heat for 10-13min, and naturally cooling to room temperature to obtain a copper zinc tin germanium selenium absorption layer film with germanium gradient; the preparation method can form concentration gradient of Ge on the back surface to form an electron blocking layer to block the recombination of carriers at the interface of the back surface, thereby improving the carrier collection efficiency of the Cu-Zn-Sn-Se-based film and further improving the performance of the film.

Description

Preparation method of copper zinc tin germanium selenium absorption layer film with germanium gradient
Technical Field
The invention relates to the technical field of new energy sources of photoelectric materials, in particular to a preparation method of a copper zinc tin germanium selenium absorption layer film with a germanium gradient.
Background
In the research and development of solar cells in recent decades, the first generation of silicon solar cells has gradually progressed into saturation phase, so researchers have turned the goal to new materials, new types of solar cells, with higher conversion efficiency and lower cost, namely second generation solar cells: thin film solar cells, such as single junction Cu (In, ga) Se 2 (CIGS), cdTe, and GaAs, which developed rapidly in later studies, and achieved significant achievements. But these film materialsThe materials used In the material comprise toxic heavy metal cadmium (Cd), rare metals tellurium (Te), indium (In), gallium (Ga) and the like, so that the mass production application and future development prospect of the materials are limited, and compared with a high-efficiency CIGS thin film battery, cu 2 ZnSnSe 4 The (CZTSe) thin film battery lacks not only an energy band gradient that is modulated by a composition gradient inside the absorber layer to facilitate carrier transport, but also fails to reduce carrier interfacial recombination by inversion of a buried PN junction at the absorber layer surface. And for Cu 2 ZnSnSe 4 For (CZTSe) thin film batteries, cu is prepared by incorporating a germanium (Ge) element of the same family in place of part of the Sn element 2 ZnSn1-xGexSe 4 (CZTSSe) can be used to adjust the forbidden band width, and CZTSSe has a band gap of more than 10 4 cm -1 The light absorption coefficient of the film solar cell is rich in the crust, so that the film solar cell has the advantages of rich resources, low raw material cost and the like, and is expected to become one of the best choices of the film solar cell of the new generation.
In the team researching the CZTSe film, the M.Buffere team of the university of Belgium in 2015 adopts magnetron sputtering Cu/Zn metal targets, adopts electron beam evaporation to evaporate a Ge layer, researches the influence of different selenizing temperatures and deposition sequences on the performance of the CZTSe film, and finally obtains the photoelectric conversion efficiency of 0.3 percent; the influence of Ge layers with different thicknesses on a CZTGSe thin film battery is studied by using a magnetron sputtering metal target to prepare a prefabricated layer and depositing the Ge layers with different thicknesses on the top of the prefabricated layer by utilizing a thermal evaporation method, and the photoelectric conversion efficiency of the CZTGSe thin film battery with the optimal Ge thickness is 10.6 percent. But still do not meet the demands for thin film batteries.
Therefore, the invention provides a preparation method of a copper zinc tin germanium selenium absorbing layer film with a germanium gradient, which is based on a blocking mechanism of a molybdenum (Mo) blocking layer on a fast diffusion metal, and the carrier collection efficiency of the copper zinc tin selenium base film is improved by inhibiting the diffusion speed of the fast diffusion metal Ge into the copper zinc tin selenium base film, so that the copper zinc tin germanium selenium absorbing layer film with the Ge component gradient is formed on the back surface, and the performance of the film is further improved.
Disclosure of Invention
Therefore, the invention aims to provide a preparation method of a copper zinc tin germanium selenium-based film with a germanium gradient, which can form a concentration gradient of Ge on the back surface, and the conduction band of the back surface is bent upwards due to the formation of the Ge concentration gradient so as to form an electron blocking layer, so that the recombination of carriers at the interface of the back surface is blocked, the carrier collection efficiency of the copper zinc tin selenium-based film is improved, and the performance of the film is further improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the copper zinc tin germanium selenium absorption layer film with the germanium gradient specifically comprises the following steps:
(1) Pretreatment of a substrate: cleaning and soaking the substrate, and drying for later use;
(2) Preparation of molybdenum layer and germanium layer: sequentially depositing a first molybdenum layer, a germanium layer and a second molybdenum layer on the pretreated substrate;
(3) Preparing a copper zinc tin sulfur prefabricated layer: performing multi-period step-by-step deposition on the second molybdenum layer according to the sequence of ZnS, cuS, sn, cuS to obtain a copper zinc tin sulfur prefabricated layer;
(4) Preparing a copper zinc tin germanium selenium absorption layer film: and (3) carrying out heat treatment on the substrate after the preparation of the copper zinc tin sulfur prefabricated layer in the step (3) at 210 ℃ for 30min, then placing the substrate and selenium powder into a selenizing furnace, heating from room temperature to 550 ℃ at a heating rate of 20 ℃/min, preserving heat for 10-13min, and naturally cooling to room temperature to obtain the copper zinc tin germanium selenium absorption layer film with the germanium gradient.
The method is based on a blocking mechanism of the Mo blocking layer on the rapid diffusion metal, and forms the copper zinc tin germanium selenium film with the Ge component gradient on the back surface by inhibiting the diffusion speed of the rapid diffusion metal Ge into the copper zinc tin selenium-based film.
In the preparation process of the CZTSe prefabricated layer film, on one hand, a small amount of Ge element is diffused from the bottom Mo layer to be doped with Sn element which is substituted, so that the forbidden bandwidth of the prepared film can be effectively increased, the band gap width of the back absorption layer is increased, and further the diffusion of electrons to the back is blocked; on the other hand, the work function of Mo is smaller than that of the CZTSe absorption layer, and the work function of the back electrode can be properly increased due to the doping of Ge, so that the energy band arrangement of metal and semiconductor is optimized, the collection of carriers is facilitated, and the efficiency of the thin film solar cell is improved.
Preferably, the substrate is a soda lime glass substrate.
Preferably, the step of washing and soaking in the step (1) is as follows: the step of cleaning and soaking in the step (1) is as follows: sequentially cleaning the substrate by using detergent and washing powder, then ultrasonically cleaning the substrate by using acetone and alcohol, then soaking the substrate in potassium dichromate solution for 8-10h, and finally ultrasonically cleaning by using deionized water.
Preferably, the ultrasonic cleaning time is 30min, and the concentration of the potassium dichromate solution is 0.4mol/L.
The glass is cleaned by adopting the steps, so that not only can the dirt generated in the production process of the soda-lime glass be removed, but also the greasy dirt and the like on the surface of the glass can be removed, the high dryness of the glass substrate is ensured, and the electrode characteristic with higher quality is realized.
Preferably, the deposition is magnetron sputtering deposition.
The sample film is deposited by adopting a magnetron sputtering method under a low vacuum condition, so that higher cleanliness can be tested, and the influence of external impurities on the film quality is reduced.
Preferably, in the step (2), the thickness of the first molybdenum layer is 0.8 μm, and the thickness of the second molybdenum layer is 0.3 μm.
The first molybdenum layer improves the adhesion between the Mo electrode and the glass, and the second molybdenum layer can effectively reduce the diffusion of Ge element to the absorption layer film, thereby being beneficial to forming the composition gradient of the Ge element.
Preferably, the sputtering power of the germanium layer in the step (2) is 25W, and the deposition time is 20min.
When the sputtering power of the Ge layer is fixed to be 25W and the deposition time is different, the research shows that the obtained sample film can better realize the composition gradient of the Ge element when the deposition time is 20min.
Preferably, the specific steps of each of said cycles are: and sputtering and depositing targets on the second molybdenum layer according to the sequence of ZnS, cuS, sn, cuS, wherein the sputtering power of each target is 50W, and the sputtering time is 48min, 41min, 14min and 41min in sequence.
Preferably, the thickness of the copper zinc tin sulfide preformed layer in step (3) is 1.2 μm.
The thickness of the copper zinc tin sulfur prefabricated layer is 1.2 mu m, the thickness of the selenized absorption layer film can be increased to 1.5-2 mu m, solar spectrum can be absorbed more efficiently, and photon loss is reduced.
Preferably, in the step (3), the molar relationship among the Cu, the Zn, and the Sn element in the copper-zinc-tin-sulfur preformed layer satisfies: cu/zn+sn=0.65, zn/sn=1.
Cu inhibition by designing a preformed composition ratio deviating from a chemical composition ratio Zn The number of inverse structural defects and the number of Sn-related deep level defects are reduced while conforming to the composition range of CZTSe thin film solar cells of highest photoelectric conversion efficiency.
The copper zinc tin germanium selenium absorption layer film with the germanium gradient is applied to a solar cell.
According to the invention, the CZTSe film with the component gradient is prepared, so that the recombination of carriers can be reduced, better film quality can be obtained, and further, a more efficient film solar cell is realized.
Compared with the prior art, the invention discloses a preparation method of a copper zinc tin germanium selenium absorption layer film with a germanium gradient, which has the following technical effects:
according to the invention, the energy band gradient which is regulated by the component gradient and is beneficial to carrier transportation is realized through the doping position of Ge element and proper annealing condition, so that the copper zinc tin germanium selenium absorbing layer film material with the germanium gradient is prepared, and the film is formed due to the Ge concentration gradient, so that the conduction band of the back surface is bent upwards, and then an electron blocking layer is formed, the recombination of carriers at the interface of the back surface is blocked, the carrier collection efficiency of the copper zinc tin selenium-based film is improved, and the performance of the film is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a band alignment diagram of a Cu-Zn-Sn-Ge-Se absorber film with a Ge gradient prepared in example 1;
FIG. 2 is a surface view (a) of SEM of a Cu-Zn-Sn-Ge-Se absorber film with Ge gradient prepared in example 1;
FIG. 3 is a cross-sectional view (b) of an SEM of a Cu-Zn-Sn-Ge-Se absorber film with a Ge gradient prepared in example 1;
FIG. 4 is a grazing incidence angle XRD pattern of a Cu-Zn-Sn-Ge-Se absorber film with a Ge gradient prepared in example 1;
fig. 5 is a J-V graph of the solar cell of the application example and the comparative example.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the copper zinc tin germanium selenium absorption layer film with the germanium gradient specifically comprises the following steps:
(1) Pretreatment of a substrate: sequentially cleaning a sample of a soda-lime glass substrate by using cleaning powder and washing powder, and then ultrasonically cleaning the bottom by using acetone and alcohol, wherein the ultrasonic time is 30min, then soaking the bottom in 0.4mol/L potassium dichromate for 8-10h, and then ultrasonically cleaning the bottom by using deionized water for 30min and drying the soda-lime glass by using nitrogen for later use;
(2) Preparation of molybdenum layer and germanium layer: putting the pretreated soda lime glass into a magnetron sputtering system, firstly depositing a first molybdenum layer (back electrode layer) with the thickness of 0.8 mu m on the soda lime glass, then sputtering and depositing a Ge layer on the first molybdenum layer, wherein the sputtering power of a Ge target is 25W, the deposition time is 20min, and finally, depositing a second molybdenum layer (back electrode layer) with the thickness of 0.3 mu m on the Ge layer;
(3) Preparing a copper zinc tin sulfur prefabricated layer: performing multi-period step-by-step sputtering on the second molybdenum layer in the step (2) according to the sequence of ZnS, cuS, sn, cuS, and depositing a copper zinc tin sulfide prefabricated layer film with the thickness of 1.2 mu m; wherein the period is 3, the sputtering power of each target is 50W, and the sputtering time of ZnS and CuS, sn, cuS is 48min, 41min, 14min and 41min in sequence; the mol ratio of Cu, zn and Sn elements is as follows: cu/zn+sn=0.65, zn/sn=1;
(4) Preparing a copper zinc tin germanium selenium absorption layer film: and (3) carrying out heat treatment on the soda lime glass prepared by the copper zinc tin sulfur prefabricated layer in the step (3) at the temperature of 210 ℃ for 30min under the protection of argon, then placing the soda lime glass and selenium powder into a graphite boat, finally placing the graphite boat into a selenizing furnace, heating at the heating rate of 20 ℃/min from room temperature, raising the temperature to 550 ℃, maintaining for 10-13min, and naturally cooling to the room temperature to obtain the copper zinc tin germanium selenium absorbing layer film with the germanium gradient, wherein EDS data results of the film are shown in Table 1.
TABLE 1 EDS data for copper zinc tin germanium selenium absorbing layer films prepared in example 1
Figure BDA0002556047850000061
Figure BDA0002556047850000071
As is clear from the above table data, the deposition time used in the present invention was 20min because the amount of Ge/(Ge+Sn) incorporated was about 7.05% when the deposition time was 20min.
In addition, fig. 1 is an energy band alignment diagram of the cu-zn-sn-Ge-se absorbing layer film with a germanium gradient prepared in example 1, and it can be seen from the energy band diagram of the absorbing layer that when Ge is doped into the CZTSe film, the conduction band position of the back surface can be increased, so as to prevent the transport of photo-generated electrons to the Mo electrode, and reduce the recombination of carriers; as can be seen from the surface and the sectional views of the CZTSe thin films shown in the figures 2 and 3, the grains on the surface of the sample are relatively compact, and the Mo layer in longitudinal distribution has layering phenomenon, but the grains are relatively good in longitudinal growth; FIG. 4 is a grazing incidence angle XRD pattern of the Cu-Zn-Sn-Ge-Se absorber film with Ge gradient prepared in example 1, as can be seen by testing XRDs at different incidence angles and locally amplifying the main peak (112) of the film, the more the main peak position shifts to the right as the incidence angle becomes larger, indicating that the more Ge content at that depth, the determination is made to prepare a CZTGSe film with Ge composition gradient; from the above, the preparation method can prepare the copper zinc tin germanium selenium absorption layer film with germanium gradient.
Application example
A solar cell was prepared by using the copper zinc tin germanium selenium absorbing layer thin film having a germanium gradient obtained in example 1 according to the prior art, and various parameters were measured, and the results are shown in fig. 4 and table 2.
Comparative example
In the same manner as in the application example, a solar cell was prepared using a copper zinc tin selenium absorbing layer film without germanium, and various parameters were measured, and the results are shown in fig. 4 and table 2.
Table 2 results of solar cell parameters for examples and comparative examples
Sanple V oc (mv) J sc (mA/cm 2 ) FF(％) η(％) R s (Ω·cm 2 ) R s (Ω·cm 2 )
Cell1 360 20.31 28.6 2.03 15.9 89.2
Cell2 373 34.04 29.7 3.69 10.2 132.5
As can be seen from the data in fig. 4 and table 2, when Ge is doped, the current density of the CZTGSe thin film solar cell is much higher than that of the CZTSe thin film solar cell, and the efficiency of the CZTGSe thin film solar cell is improved by about 80% compared with that of a pure CZTSe thin film solar cell, so that the superiority of the performance of preparing the copper zinc tin germanium selenium absorbing layer thin film solar cell with a germanium gradient can be seen.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (4)

1. The preparation method of the copper zinc tin germanium selenium absorption layer film with the germanium gradient is characterized by comprising the following steps of:
pretreatment of a substrate: cleaning and soaking the substrate, and drying for later use;
preparation of molybdenum layer and germanium layer: sequentially depositing a first molybdenum layer, a germanium layer and a second molybdenum layer on the pretreated substrate; the thickness of the first molybdenum layer is 0.8 mu m, the thickness of the second molybdenum layer is 0.3 mu m, the sputtering power of the germanium layer is 25W, and the deposition time is 20min;
preparing a copper zinc tin sulfur prefabricated layer: depositing on the second molybdenum layer according to the sequence of ZnS, cuS, sn, cuS to obtain a copper zinc tin sulfide prefabricated layer; the deposition is periodic step-by-step sputtering deposition, the number of the periods is 3, and the specific steps of each period are as follows: sputtering and depositing targets on the second molybdenum layer according to the sequence of ZnS, cuS, sn, cuS, wherein the sputtering power of each target is 50W, and the sputtering time is 48min, 41min, 14min and 41min in sequence; the thickness of the copper zinc tin sulfur prefabricated layer is 1.2 mu m, and the molar relation of Cu, zn and Sn elements in the copper zinc tin sulfur prefabricated layer meets Cu/Zn+Sn=0.65 and Zn/Sn=1;
preparing a copper zinc tin germanium selenium absorption layer film: and (3) carrying out heat treatment on the substrate after the preparation of the copper zinc tin sulfur prefabricated layer is finished at 210 ℃ for 30min, then placing the substrate and selenium powder into a selenizing furnace, heating from room temperature to 550 ℃ at a heating rate of 20 ℃/min, preserving heat for 10-13min, and naturally cooling to room temperature to obtain the copper zinc tin germanium selenium absorption layer film with the germanium concentration gradient.
2. The method for preparing a copper zinc tin germanium selenium absorbing layer film with a germanium gradient according to claim 1, wherein the substrate is a soda lime glass substrate.
3. The method for preparing the copper zinc tin germanium selenium absorbing layer film with the germanium gradient according to claim 1, wherein the step of cleaning and soaking is characterized in that: sequentially cleaning the substrate by using detergent and washing powder, then ultrasonically cleaning the substrate by using acetone and alcohol, then soaking the substrate in potassium dichromate solution for 8-10h, and finally ultrasonically cleaning by using deionized water.
4. The method for preparing a copper zinc tin germanium selenium absorbing layer film with a germanium gradient according to claim 3, wherein the ultrasonic cleaning time is 30min, and the concentration of the potassium dichromate solution is 0.4mol/L.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009134211A1 (en) * 2008-04-29 2009-11-05 Agency For Science, Technology And Research Inorganic graded barrier film and methods for their manufacture
WO2019246095A1 (en) * 2018-06-21 2019-12-26 Applied Materials, Inc. Diffusion barrier films enabling the stability of lithium

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI382545B (en) * 2008-09-19 2013-01-11 Nexpower Technology Corp A stacked-layered thin film solar cell with a photoconductive layer having band gradient and a manufacturing method thereof
US20120031492A1 (en) * 2010-08-04 2012-02-09 Miasole Gallium-Containing Transition Metal Thin Film for CIGS Nucleation
US20120097234A1 (en) * 2010-10-26 2012-04-26 International Business Machines Corporation Using Diffusion Barrier Layer for CuZnSn(S,Se) Thin Film Solar Cell
KR20130045516A (en) * 2011-10-26 2013-05-06 한국과학기술연구원 Thin film solar cell and method of manufacturing the same
US9013021B2 (en) * 2011-12-21 2015-04-21 Intermolecular, Inc. Optical absorbers
CN102820346B (en) * 2012-08-09 2015-04-15 深圳先进技术研究院 Copper zinc tin germanium selenium thin film, preparation method thereof and copper zinc tin germanium selenium thin film solar cell
CN102820345B (en) * 2012-08-09 2015-03-04 深圳先进技术研究院 Copper zinc tin germanium selenium thin film, preparation method thereof and copper zinc tin germanium selenium thin film solar cell
KR101389832B1 (en) * 2012-11-09 2014-04-30 한국과학기술연구원 Cigs or czts based film solar cells and method for preparing thereof
CN103346201B (en) * 2013-05-24 2016-11-23 徐东 Mix copper zinc tin sulfur selenium method for manufacturing thin film, thin film and the solaode of germanium
KR101708282B1 (en) * 2014-09-29 2017-02-20 이화여자대학교 산학협력단 Solar cell using -based film and preparing method of the same
US10134929B2 (en) * 2015-10-14 2018-11-20 International Business Machines Corporation Achieving band gap grading of CZTS and CZTSe materials
US10062792B2 (en) * 2016-05-16 2018-08-28 Solar-Tectic Llc Method of making a CZTS/silicon thin-film tandem solar cell
CN107195582B (en) * 2017-07-03 2019-04-12 北方工业大学 Diffusion barrier layer preparation method and copper interconnection structure
CN108305906B (en) * 2018-02-08 2019-09-03 北京铂阳顶荣光伏科技有限公司 The preparation method of solar battery obsorbing layer and the preparation method of solar battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009134211A1 (en) * 2008-04-29 2009-11-05 Agency For Science, Technology And Research Inorganic graded barrier film and methods for their manufacture
WO2019246095A1 (en) * 2018-06-21 2019-12-26 Applied Materials, Inc. Diffusion barrier films enabling the stability of lithium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
铜铟镓硒薄膜太阳电池吸收层制备方法及性能分析;刘洋;;科技创新与应用(第14期);全文 *

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