CN112071946A - Preparation method of thin-film solar cell - Google Patents

Preparation method of thin-film solar cell Download PDF

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CN112071946A
CN112071946A CN201910421524.0A CN201910421524A CN112071946A CN 112071946 A CN112071946 A CN 112071946A CN 201910421524 A CN201910421524 A CN 201910421524A CN 112071946 A CN112071946 A CN 112071946A
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stainless steel
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姚俊奇
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Hongyi Technology Co.,Ltd.
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Beijing Apollo Ding Rong Solar Technology Co Ltd
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    • 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
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    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
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Abstract

The application relates to a preparation method of a thin film solar cell, which comprises the following steps: carrying out alkaline blackening treatment on the stainless steel substrate, wherein the alkaline blackening treatment is carried out in an ultrasonic oscillation environment; depositing a back electrode on the stainless steel substrate after the alkaline blackening treatment; depositing an absorption layer on the back electrode; depositing a buffer layer on the absorber layer; and depositing a window layer on the buffer layer. According to the preparation method of the thin-film solar cell, alkaline blackening treatment is carried out on the stainless steel substrate, a compact oxide film is generated by oxidation treatment of metal elements of stainless steel, and a diffusion barrier of the metal elements is formed, so that diffusion of elements such as Fe and Cu in the stainless steel to a Mo electrode and a CIGS absorption layer is better blocked in the subsequent CIGS high-temperature selenization process. Meanwhile, ultrasonic oscillation is introduced in the alkaline blackening process, the loose film part with poor binding force is removed, a compact and uniform film is realized, and the blocking effect of the oxide film is improved.

Description

Preparation method of thin-film solar cell
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of a thin-film solar cell.
Background
The stainless steel foil becomes the preferred material of the substrate of the flexible Copper Indium Gallium Selenide (CIGS) thin-film solar cell at present due to the advantages of excellent high-temperature performance, good flexibility, light weight, low price, suitability for a roll-to-roll process of large-scale production and the like.
However, elements such as Fe and Cu in the stainless steel substrate can diffuse into the CIGS absorber layer through the molybdenum (Mo) electrode under the high-temperature preparation condition of the CIGS absorber layer, and deep-level defects are formed in the CIGS, which affects the crystallization quality of the CIGS, and thus affects the photoelectric performance of the cell. Therefore, a suitable barrier system is usually prepared between the stainless steel substrate and the Mo electrode to prevent diffusion of elements in the substrate.
The barrier layers in CIGS cells in the current patent literature are metallic or non-metallic layers deposited by Physical Vapor Deposition (PVD) or Chemical Vapor Deposition (CVD) techniques on a smooth stainless steel foil surface. For example, there is a document disclosing a flexible CIGS cell with a three-layer structure of barrier layer, a bottom layer near the stainless steel substrate made of titanium, chromium, titanium nitride, or tantalum nitride, a middle layer made of any one of titanium nitride, tantalum nitride, tungsten nitride, or zirconium nitride, and an electrode layer made of titanium, chromium, or titanium nitride, and the diffusion barrier layer obtained by screening the structure of the diffusion barrier layer and the composition of each structure can effectively block the impurity elements of the stainless steel foil from entering the absorption layer, thereby improving the cell performance. However, the three-layer structure is relatively complex and the production cost is too high.
The literature discloses that a 1-2 μm chromium (Cr) diffusion barrier layer is used as a barrier layer of a flexible CIGS cell, and the conversion efficiency of the flexible CIGS cell is improved by inhibiting the diffusion of elements such as Fe and Cu on a stainless steel substrate by a Cr monolayer. The defect of the technology is that the single layer Cr is too thin, the barrier effect on the diffusion of elements such as Fe, Cu and the like is limited, and the excessive thickness consumes larger time and material cost in production.
The literature discloses that the insulating barrier layer in the flexible CIGS cell is a laminated structure of one or more nitride or oxide layers, a compound film is deposited on a stainless steel substrate, and then a metal film is deposited, i.e. a structural form of the stainless steel substrate/one or more compound films/metal film/Mo back electrode layer is formed, so that the inline cell assembly structure is realized by adopting the laser scribing technology through the barrier property and the insulating property of the laminated structure. The defect of the technology is that the brittleness and the fracture energy release mechanism of the pure nitrogen oxide laminated material easily cause the cracking and the demoulding of the film layer, thereby reducing the barrier effect on the diffusion of impurity elements such as Fe, Cu and the like.
The document also discloses that the diffusion barrier layer is a tungsten-titanium alloy layer, and the photoelectric performance of the flexible battery is improved by blocking the diffusion of harmful elements in the substrate.
The barrier layers in the above patent documents are all metal or nonmetal layers deposited by PVD, CVD or other techniques on the surface of a clean stainless steel foil, and a sufficient thickness is generally required to ensure a good barrier effect, and the consumption of raw materials such as the above metals or nonmetals is large, and the cost is not negligible.
Disclosure of Invention
In order to solve the technical problems, the invention provides a film deposition means for breaking through the traditional barrier layer, and the surface is densified by utilizing the oxidation treatment of the self elements of the stainless steel substrate, so that the excellent barrier property is obtained.
The specific technical scheme provided by one embodiment of the application is as follows:
a preparation method of a thin film solar cell comprises the following steps:
carrying out alkaline blackening treatment on the stainless steel substrate, wherein the alkaline blackening treatment is carried out in an ultrasonic oscillation environment;
depositing a back electrode on the stainless steel substrate after the alkaline blackening treatment;
depositing an absorber layer on the back electrode;
depositing a buffer layer on the absorber layer; and
depositing a window layer on the buffer layer.
In the preparation method of the thin-film solar cell in the embodiment of the application, the improved alkaline blackening treatment is performed on the surface of the stainless steel, the oxidation treatment of the metal elements of the stainless steel is utilized to generate the compact oxide film, and the diffusion barrier of the metal elements is formed, so that the diffusion of Fe, Cu and other elements in the stainless steel to the Mo electrode and the CIGS absorption layer is better blocked in the subsequent CIGS high-temperature selenization process. Meanwhile, ultrasonic oscillation is introduced in the alkaline blackening process, the loose film part with poor binding force is removed, a compact and uniform film structure is realized, and the blocking effect of the oxide film is improved. The method can reduce the dependence on raw materials such as metal materials in the barrier layer, and is simple, so that a feasible way is provided for improving the photoelectric conversion efficiency of the CIGS solar cell and reducing the production cost of the photovoltaic cell.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a flowchart of a method for manufacturing a thin film solar cell according to an embodiment of the present invention;
fig. 2 is a flowchart of a method for manufacturing a thin film solar cell according to another embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The invention provides a preparation method of a thin film solar cell. Fig. 1 shows a flowchart of a method for manufacturing a thin film solar cell according to an embodiment of the present invention. As shown in fig. 1, the method for manufacturing a thin film solar cell includes the following steps:
first, step S100 is performed: and carrying out alkaline blackening treatment on the stainless steel substrate, wherein the alkaline blackening treatment is carried out in an ultrasonic oscillation environment.
Wherein the stainless steel liningThe substrate is a chromium stainless steel substrate, a chromium-nickel-molybdenum stainless steel substrate, an ultra-low carbon stainless steel substrate, a high molybdenum stainless steel substrate and a high purity stainless steel substrate. The oxide film material finally generated on the substrate can be Fe correspondingly according to the different components of the stainless steel substratexOy、CrxOy、MoxOy、MnxOy、AlxOy、NixOyAnd the like.
The alkaline blackening treatment is one of surface oxidation treatment methods, and is characterized by that the stainless steel substrate is placed in the solution of alkali and oxidant, and heated and oxidized at a certain temp. so as to make the surface of stainless steel produce a layer of uniform and compact oxide film. In one embodiment of the present application, the blackening solution used in the alkaline blackening treatment contains NaOH and NaNO2. Wherein NaOH is used as alkali, NaNO2As an oxidizing agent. To produce Fe3O4For example, in the blackening solution, NaOH has the following three functions: slightly corroding the surface of the stainless steel substrate to separate out ferrous ions and promote the formation of an oxide film; the boiling point of the solution is increased, and the temperature required by the blackening treatment process is ensured; the deoiling effect is beneficial to the generation of an oxide film. NaNO2The function of (1): mainly plays an oxidizing role, and reacts with alkali and iron ions to generate an oxide film.
The content of each component in the blackening solution is critical to the result of the blackening treatment. For example, if the NaOH content is too low, the temperature of the blackening solution is not raised, and the normal temperature required for blackening cannot be reached, the obtained oxide film is too thin, and the blackening and protection properties are poor, while if the NaOH content is too high, the generated oxide film is promoted to be dissolved, so that the generated oxide film is damaged, and the defects of looseness and porosity are easily caused. In the present application, the mass of NaOH is 10 to 50% of the total mass of the blackening solution, and may be, for example, 15%, 25%, 35%, or 45%.
Further, NaNO is used as a main mediator in the blackening solution2The content also has a great influence on the formation and quality of the oxide film. For example, NaNO2When the content is higher, the oxidation speed is higher, and the film is formedThe layer is compact and firm, but the thickness of the film is thin; NaNO2At lower contents, the oxidation rate is slower, the film thickness is thicker, but it is looser and easily peels off. In this application, NaNO2The amount of (b) is 1 to 20% by mass, for example, 5%, 10% or 15% by mass of the total mass of the blackening solution.
Preferably, the blackening solution may further contain Na3PO4It is possible to improve the quality of the oxide film formed, to make the oxide film formed fine, and to improve the corrosion resistance. Adding small amount of Na3PO4The quality improvement of the film layer can be realized. In this application, Na3PO4The amount of (b) is 0 to 10% by mass of the total mass of the blackening solution, and may be, for example, 2%, 4%, 6%, or 8%.
The blackening solution contains NaOH and NaNO2And Na3PO4The remainder being water. Namely, the blackening solution is composed of the following substances in percentage by mass: 10-50% of NaOH and 1-20% of NaNO20-10% of Na3PO4And 30-60% of water. For example, the blackening solution may be composed of: 40% NaOH, 10% NaNO250% of water, and can also be: 30% NaOH, 15% NaNO25% of Na3PO4And 50% water.
In addition to the composition of the blackening solution, the temperature of the blackening treatment also has an effect on the formation of an oxide film. When the temperature is raised, the oxidation speed is correspondingly accelerated, the thickness of the oxidation film is thick and compact, but when the temperature is too high, the solubility of the oxidation film in alkali liquor is improved, the oxidation speed is slowed down, and the film layer is loose. When the temperature is too low, the oxidation is insufficient, the film layer is thin, and the corrosion resistance is poor.
The treatment time of the blackening treatment is related to the chemical composition of the stainless steel. For example, when the carbon content of steel is low, the oxidation film has good corrosion resistance, but is difficult to oxidize, and the blackening treatment time is long.
In the application, the treatment temperature of the alkaline blackening treatment is 100-170 ℃, and the treatment time is 1-30 minutes. For example, the blackening treatment is carried out for 20 minutes under the condition of 120 ℃, so that the generated oxide film layer is ensured to be relatively dense.
Due to some complex reactions in the blackening treatment process, besides the oxide film, the stainless steel substrate can adsorb other products, and the products are too much to be beneficial to the growth of the final film layer, so that the binding force is reduced. Therefore, in the present application, the alkaline blackening treatment is performed in an ultrasonic oscillation environment. By ultrasonic oscillation, these excess products can be cleaned off, and the final oxide film formed on the stainless steel substrate is a dense and strong-bonding oxide film. In order to remove the film with poor binding force and retain the oxide film with strong binding force, in the ultrasonic oscillation of the ultrasonic vibration ultrasonic frequency is 10-50KHz, and the ultrasonic power density is 0.2-3W/cm2。
Meanwhile, considering that the generation of the oxide film needs a certain time, if the ultrasonic oscillation is carried out all the time, the adhesion of the oxide film in the reaction process is possibly difficult, and the film deposition speed is greatly reduced. Therefore, the ultrasonic oscillation in this application sets up to intermittent type nature and vibrates, i.e. ultrasonic oscillation a period of time stops ultrasonic oscillation, carries out ultrasonic oscillation once more at certain interval. In one embodiment of the present application, the oscillation time is controlled to perform ultrasonic oscillation every 10-60s, and the oscillation time is 3-10 s.
After step S100, step S200 is performed: and depositing a back electrode on the stainless steel substrate after the alkaline blackening treatment.
After the alkaline blackening treatment is finished, an oxide film layer with the thickness of 10nm-2.5 mu m is generated on the stainless steel substrate, and then when the back electrode is prepared on the substrate, the film layer forms a diffusion barrier of metal elements and blocks Fe, Cu and other elements in the stainless steel substrate from diffusing to the back electrode and the CIGS absorption layer.
The material of the back electrode layer may be molybdenum, titanium, chromium, copper, or one of AZO, BZO, and ITO, preferably molybdenum. The molybdenum has a loose structure, and the adhesion between the back contact layer and the stainless steel substrate can be improved. In addition, the resistivity of the low-resistance molybdenum metal layer is small, so that collection and conduction of photo-generated current are facilitated, and the series resistance of the battery can be reduced. The back electrode can be formed on the stainless steel substrate by adopting a magnetron sputtering coating mode.
After step S200, step S300 is performed: an absorber layer is deposited on the back electrode.
Wherein the absorption layer is a P region of the thin film solar cell, which can be selected from any one of the following: CIGS, copper zinc tin sulfide thin film (CZTS), copper indium sulfide thin film (CIS), copper gallium selenide thin film (CGS), copper indium selenide thin film (CIS), CIGS being preferred in the present application. The absorber layer may be prepared on the surface of the back electrode remote from the stainless steel substrate, such as by magnetron sputtering or co-evaporation.
After step S300, step S400 is performed: depositing a buffer layer on the absorber layer.
In the step S400, after the absorption layer is prepared, the buffer layer is prepared on the surface of the absorption layer away from the back electrode layer by using a chemical water bath deposition method or a sputtering method. The buffer layer can be made of one of zinc sulfide, cadmium sulfide and indium sulfide. When the absorber layer is CIGS, the buffer layer is preferably a cadmium sulfide (CdS) buffer layer thin film. The CdS film can be matched with the forbidden band width between the absorption layer and the window layer, so that the band gap step and the lattice mismatch rate between the two layers are reduced.
Finally, step S500 is performed: depositing a window layer on the buffer layer.
The window layer comprises a high-resistance layer and a transparent conductive layer, specifically, the high-resistance layer is intrinsic ZnO, and the transparent conductive layer can be an ITO layer or an AZO layer. The intrinsic ZnO film has a wider band gap (about 3.3 eV-3.6 eV), higher light transmittance and resistivity, and can transmit most of solar spectrum. In a CIGS solar cell, the high resistance layer and the buffer layer constitute an N region. And preparing the window layer on the surface of the high-resistance layer far away from the buffer layer by adopting a magnetron sputtering method. The window layer can be prepared by a magnetron sputtering method, namely, an intrinsic ZnO layer is sputtered and deposited on the buffer layer, and an ITO layer or an AZO layer is sputtered and deposited on the intrinsic ZnO layer.
The oxide film layer formed after the alkaline blackening treatment can be used as a barrier layer independently or can be combined with barrier layers of other structures. Fig. 2 shows a flowchart of a method for manufacturing a thin film solar cell according to another embodiment of the present invention. As shown in fig. 2, after step S100 and before step S200, the method further includes step S100': and depositing an impurity barrier layer on the stainless steel substrate.
The impurity barrier layer is one or more of a metal layer, a metal oxide layer and a metal nitride layer. For example, the impurity blocking layer may be a metal layer, and the metal may be molybdenum, chromium, titanium, aluminum, nickel, or the like. The impurity blocking layer may also be a metal oxide layer or a metal nitride layer, and may be, for example, molybdenum nitride, aluminum nitride, nickel nitride, molybdenum oxide, nickel oxide, or the like. The impurity barrier layer may also be a composite structure of a metal layer and a metal oxide layer, or a composite structure of a metal layer and a metal nitride layer, for example, composed of a layer of chromium and a layer of molybdenum nitride. Wherein the thickness of the impurity blocking layer is set to 10nm to 2.5 μm, and for example, may be 100nm, 300nm, 500nm, 700 nm.
In step S100', an impurity barrier layer may be formed on a stainless substrate by vapor deposition. Among them, the Vapor Deposition method can be generally classified into two types, one is a Physical Vapor Deposition (PVD) method, and the other is a Chemical Vapor Deposition (CVD) method. In this step, a barrier layer may be formed on the stainless steel substrate by using a PVD method, or may be formed on the stainless steel substrate by using a CVD method, which is not limited in this embodiment of the present invention. For example, when the impurity blocking layer is formed on the stainless steel substrate by PVD, a magnetron sputtering coating method, a multi-arc ion coating method, or a thermal evaporation coating method may be used.
It should be understood by those skilled in the art that fig. 1 and 2 are merely schematic diagrams illustrating the manufacturing process of the thin film solar cell of a conventional structure, and the thin film solar cell may include other structures. For example, the thin film solar cell may further include a top electrode disposed on the window layer, and an anti-reflective layer disposed on the top electrode. The antireflection layer can be used for reducing the reflection of light and increasing the absorption of the light, so that the photoelectric conversion performance of the thin-film solar cell is further improved. For example, a top electrode may be formed on the window layer by a magnetron sputtering coating method, and an anti-reflection layer may be formed on the top electrode by an evaporation method.
The magnetron sputtering coating mode, the chemical water bath deposition mode, the co-evaporation mode and the evaporation mode are all common modes in the prior art, and the operation process and the operation parameters are not described in detail herein.
In summary, the preparation method of the solar cell provided by the embodiment of the application breaks through a film deposition means of a traditional barrier layer, and a dense oxide film is generated by performing alkaline blackening treatment on a stainless steel substrate and utilizing oxidation treatment of metal elements of stainless steel, so that a diffusion barrier of the metal elements is formed, and diffusion of elements such as Fe and Cu in the stainless steel to a Mo electrode and a CIGS absorption layer is better blocked in a subsequent CIGS high-temperature selenization process. Meanwhile, the film layer material with poor binding force and looseness generated in the blackening treatment process is removed through ultrasonic oscillation, and finally a compact oxide film is generated on the stainless steel substrate. The preparation method of the cell reduces the cost requirement on the material of the barrier layer, also reduces the requirement on the coating equipment, and provides a feasible way for saving the production cost of the photovoltaic cell.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The preparation method of the thin film solar cell is characterized by comprising the following steps:
carrying out alkaline blackening treatment on the stainless steel substrate, wherein the alkaline blackening treatment is carried out in an ultrasonic oscillation environment;
depositing a back electrode on the stainless steel substrate after the alkaline blackening treatment;
depositing an absorber layer on the back electrode;
depositing a buffer layer on the absorber layer; and
depositing a window layer on the buffer layer.
2. The method according to claim 1, wherein the thin film solar cell is manufactured by a method comprising the steps of,
the treatment temperature of the alkaline blackening treatment is 100-170 ℃, and the treatment time is 1-30 minutes.
3. The method according to claim 1, wherein the thin film solar cell is manufactured by a method comprising the steps of,
in the alkaline blackening treatment, the blackening solution used comprises the following substances in percentage by mass: 10-50% of NaOH and 1-20% of NaNO20-10% of Na3PO4And 30-60% of water.
4. The method according to claim 1, wherein the thin film solar cell is manufactured by a method comprising the steps of,
in the ultrasonic oscillation, the ultrasonic frequency is 10-50KHz, and the ultrasonic power density is 0.2-3W/cm2。
5. The method according to claim 1, wherein the thin film solar cell is manufactured by a method comprising the steps of,
the ultrasonic oscillation is intermittent oscillation, wherein the ultrasonic oscillation is carried out once every 10-60s, and each oscillation is carried out for 3-10 s.
6. The method according to claim 1, wherein the thin film solar cell is manufactured by a method comprising the steps of,
the stainless steel substrate is a chromium stainless steel substrate, a chromium-nickel-molybdenum stainless steel substrate, an ultra-low carbon stainless steel substrate, a high molybdenum stainless steel substrate and a high purity stainless steel substrate.
7. The method for manufacturing a thin film solar cell according to any one of claims 1 to 6, further comprising:
and after the alkaline blackening treatment is completed and before the back electrode is deposited, depositing an impurity blocking layer on the stainless steel substrate.
8. The method according to claim 7, wherein the thin film solar cell is manufactured by the method,
the impurity barrier layer is one or more of a metal layer, a metal oxide layer and a metal nitride layer.
9. The method according to claim 7, wherein the thin film solar cell is manufactured by the method,
the thickness of the impurity blocking layer is 10nm-2.5 mu m.
10. The method according to claim 7, wherein the thin film solar cell is manufactured by the method,
and depositing the impurity barrier layer on the stainless steel substrate by adopting a vapor deposition mode.
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Citations (23)

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