WO2014012383A1 - 一种铜铟镓硒薄膜太阳能电池的制备方法 - Google Patents

一种铜铟镓硒薄膜太阳能电池的制备方法 Download PDF

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WO2014012383A1
WO2014012383A1 PCT/CN2013/074096 CN2013074096W WO2014012383A1 WO 2014012383 A1 WO2014012383 A1 WO 2014012383A1 CN 2013074096 W CN2013074096 W CN 2013074096W WO 2014012383 A1 WO2014012383 A1 WO 2014012383A1
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sputtering
chamber
layer
indium gallium
substrate
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French (fr)
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林刘毓
张准
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/568—Transferring the substrates through a series of coating stations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • 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]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/22—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using physical deposition, e.g. vacuum deposition or sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3202—Materials thereof
    • H10P14/3236—Materials thereof being chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
    • H10P14/3202—Materials thereof
    • H10P14/3241—Materials thereof being conductive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3436—Deposited materials, e.g. layers characterised by the chemical composition being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of solar cells, and more particularly to a method for preparing a copper indium gallium selenide thin film solar cell.
  • the copper indium gallium selenide compound has a chalcopyrite structure and can be prepared as a material for solar power generation on a soft or rigid substrate, and the copper indium gallium selenide thin film solar cell thus produced has the advantages of high stability and low cost.
  • the available energy on the earth is becoming shorter and shorter, and it is an indisputable fact that petrochemical energy will emit carbon and sulfur oxides during use, causing air pollution and aggravating the earth's greenhouse effect, making the earth's environment worsen by climate anomalies. . Therefore, the development of pollution-free renewable energy is one of the top research projects in the world. Solar energy is a pollution-free energy source and one of the best choices for renewable energy. The development of solar energy is primarily the development of materials that produce high energy conversion into electricity.
  • the copper indium gallium selenide compound material is a compound semiconductor material having a chalcopyrite structure, which is a direct band gap material, can absorb sunlight having a large wavelength range, and has self-modulating self-composition to form a pn junction, and is recognized.
  • One of the best materials for the absorption layer of solar cells such as copper indium gallium diselenide (Cu(InGa) Se 2 ), referred to as CIGS, is the semiconductor material with the highest light absorption capability. Due to the high light absorption rate of CIGS, the thickness of the CIGS absorber layer can be 1 ⁇ 2 ⁇ . Generally, the cost of CIGS material is only 0.03 US dollars/watt, which is very competitive. It is expected that solar power generation can be the same or even lower than traditional fossil fuel power generation. Therefore, how to prepare a low-cost, high-efficiency copper indium gallium selenide solar thin film battery is one of the most worthy research topics.
  • the tunable nature of the band gap of CIGS compounds is precisely the way to achieve this.
  • the content ratio of Ga can be adjusted in the preparation of the CIGS film. Increasing the ratio of Ga, the forbidden band gap of CIGS compounds will increase.
  • selenization method (2) lamination method, (3) multi-source (two or three source) evaporation method, (4) sputtering method requires vulcanization of CIGS film in a certain process or Selenization treatment, by Sulphurization or selenization treatment, S and Se atoms can be reacted with Cu-In-Ga by diffusion to form CuInGaSe compound, which is called vulcanization or selenization.
  • the method of selenization to produce a thin film solar cell having a chalcopyrite structure has disadvantages such as a long production cycle, a large energy consumption, a large consumption of Se, a highly toxic vapor of Se, an uneven distribution of Se, a gradient of Se, and the like.
  • the above various processes are more difficult to implement in one step.
  • the three-stage co-evaporation method developed by the NREL laboratory in the United States realizes that the above-mentioned band gap gradient A or V-shaped band gap gradient is involved in the evaporation reaction in three different elements, and the process is very complicated and requires precise control in real time. Can be achieved.
  • this method can prepare a solar thin film battery with high conversion efficiency, it is disadvantageous for low-cost, large-area, and large-scale production.
  • the invention provides a method for preparing a copper indium gallium selenide thin film solar cell, comprising: a) preparing a molybdenum back electrode on a substrate;
  • the sputtering apparatus comprises: an input platform, an input cavity, and a N a sputtering chamber, an unloading chamber, an unloading platform, wherein the N sputtering chambers are cascaded together, the internal volume of the input chamber is less than or equal to the internal volume of the sputtering chamber, and the internal volume of the unloading chamber is less than or equal to the sputtering chamber Internal volume; and the substrate is transferred from the input cavity
  • the vacuum environment of the first sputtering chamber is not destroyed when it is in the first sputtering chamber, and the vacuum environment of the last sputtering chamber is not destroyed when the substrate is transferred from the last sputtering chamber to the unloading chamber.
  • a CuIn x G ai — x Se 2 alloy target is mounted in each of the N sputtering chambers, and the alloy target is sputtered at any power density between 2 and 3 W/cm 2 . to 2 minutes, the working pressure of each of the sputtering chamber are 1X10- 4 Torr, a substrate temperature chamber kept at any temperature between 200 ° C to 450 ° C;
  • the copper indium gallium selenide absorber layer is annealed in a rapid heating manner at a temperature of 400 ° C to 600 ° C and an annealing time of 55 to 90 seconds to allow copper indium gallium selenide absorption
  • the concentration of gallium in the layer forms a gradient having the highest concentration on the side of the absorption layer in contact with the molybdenum back electrode and the lowest concentration on the opposite side of the absorption layer;
  • the thickness of the copper indium gallium selenide absorber layer is from 1.5 micrometers to 2 micrometers.
  • the working pressure of the vacuum magnetron sputtering is 1-5 ⁇ 10 ⁇ 3 Torr and the Ar gas is introduced, the substrate The temperature is kept at room temperature.
  • step e in performing step e), the vacuum by RF magnetron sputtering, the target intrinsic zinc oxide, RF magnetron sputtering vacuum working pressure 1-5X10- 3 Torr, operating frequency is willing 400K ⁇ 2 z, and Ar gas is introduced, and the temperature of the substrate is kept at room temperature.
  • the target is oxygen Indium tin in 2 0 3 : Sn0 2 , ln 2 0 3 : Sn0 2 mass ratio is 9: 1, vacuum DC magnetron sputtering working pressure is 1-5 X 10 - 3 Torr, and is incorporated Ar gas of 2% to 5% 02 , the temperature of the substrate was kept at room temperature.
  • the number of the sputtering chambers is 2, 3, 4, 6, 7, or 8.
  • the gallium concentration gradient is a linear distribution.
  • the selenization-free process and the cadmium-free In 2 Se 3 or ZnS buffer layer can not only avoid the toxic gases of H 2 Se and H 2 S, but also use cadmium-free compounds, which is environmentally friendly and Reduce costs, and make the production process equipment simple, energy consumption, short production cycle and other advantages.
  • the present invention has the following advantages: all the processes of the present invention are dry process processes, and the process does not use chemical solvents and solutions.
  • the absorption layer of the solar cell can be obtained in one step to obtain a stable crystalline absorption layer, eliminating the need for an industrial process for selenization or vulcanization of the absorption layer, which greatly shortens the production cycle, reduces production equipment, and avoids production processes. Environmental pollution and potential dangers.
  • the process steps of the present invention are simplified, energy consumption is small, and thus the production cost is reduced.
  • FIG. 1 is a flow chart of a method for preparing an absorption layer of a copper indium gallium selenide thin film solar cell of the present invention
  • Figure 2 is a schematic view showing the structure of a sputtering apparatus for preparing an absorbent layer used in the present invention
  • Figure 3 is a second ion mass spectrometry (SIMS) analysis graph of the solar cell absorbing layer prepared by the method according to the present invention.
  • SIMS second ion mass spectrometry
  • Figure 1 is a flow chart showing a method of preparing a copper indium gallium selenide thin film solar cell absorber layer of the present invention, as shown in the figure:
  • the back electrode was first prepared on the substrate.
  • the substrate may be selected from soda lime glass or stainless steel sheets, and generally used is a l-3 mm thick soda lime glass or a 0.2 ⁇ thick stainless steel sheet.
  • a 0.8 ⁇ m thick molybdenum (Mo) metal was deposited as a back electrode by magnetron sputtering.
  • An absorbing layer is then prepared on the back electrode by a plurality of step-by-step sputtering methods:
  • the present invention employs a special sputtering apparatus to prepare the absorbing layer.
  • the sputtering apparatus includes: an input platform, an input chamber, a sputtering chamber 1, a sputtering chamber 2, a sputtering chamber 3, a sputtering chamber 4, a sputtering chamber 5, an unloading chamber, an unloading platform, and further includes
  • the transport mechanism is shown for sequentially transferring the substrates one by one from the input platform, and finally to the unloading platform, wherein the input platform transports the substrate to the input cavity, and then the transport mechanism feeds the sputtering chamber 1 .
  • an input chamber is provided before the sputtering chamber 1, because there is no target and/or other arrangement inside, the volume of the chamber can be designed to be small, usually smaller than the volume of the chamber of the sputtering chamber, but also It can be equal to the intracavity volume of the sputtering chamber, which functions to complete the temperature treatment (such as heating) and vacuum pretreatment that the substrate needs to be performed before being sputtered.
  • the transfer of the substrate from the input chamber to the sputtering chamber 1 does not require destruction of the vacuum environment of the sputtering chamber 1.
  • the substrate is transferred to the sputtering chamber 2, and a CuIn x G ai — x Se 2 alloy target 2 is mounted in the sputtering chamber 2, wherein 0.2 ⁇ x ⁇ 0.
  • the thickness of the deposited layer of copper indium gallium selenide is 1. 5 microns to 2 microns.
  • the working pressure in the sputtering chamber 1-5 is 1 X 10 - 4 Torr, and the temperature of the substrate is maintained at any temperature between 200 ° C and 450 ° C.
  • the sputtered substrate is transferred to the unloading chamber, and the principle of using the unloading chamber is substantially the same as that of the input chamber, that is, the transfer of the substrate from the sputtering chamber 5 to the unloading chamber does not require breaking the vacuum environment of the sputtering chamber 5, and Annealing or other temperature treatment can be done in the unloading chamber.
  • the internal volume of the unloading chamber is less than or equal to the internal volume of the sputtering chamber.
  • the substrate is then transferred to the unloading platform, which will The substrate from which the absorber layer is prepared is collected into a substrate basket.
  • the invention discloses five sputtering chambers as an example, it is known to those skilled in the art that 2-4 sputtering chambers can be used according to actual needs, and even more than 5 sputterings can be used. Cavity, for example, 6, 7, 8, or more.
  • the number of sputtering chambers is different, and/or the thickness of the deposited copper indium gallium selenide absorber layer is different, the value of x in the CuIn x G - x Se 2 alloy target is correspondingly different, which is a technique in the art. People want it.
  • Annealing is then carried out:
  • the unloading chamber is evacuated, and the copper indium gallium selenide absorber layer is annealed in a rapid heating manner at a temperature of 40 CTC to 600 ° C and an annealing time of 55 to 90 seconds. No gas is required to pass through during the annealing process.
  • the Ga ions are thermally diffused from the high concentration portion to the low concentration portion, the Ga concentration in the copper indium gallium selenide absorption layer forms a gradient on the side of the absorption layer in contact with the Mo back electrode. The highest concentration is the lowest on the opposite side of the absorbent layer.
  • the annealed copper indium gallium selenide absorption layer has a chalcopyrite structure, and local ion diffusion is performed by thermal energy to improve the crystallization state and improve the photovoltaic power generation efficiency of the main absorption layer of the solar cell.
  • the annealing process carried out by the present invention will be described in detail herein.
  • the Ga concentration forms a step inside the substrate.
  • the gradient then from the sputtering chamber 2 to the sputtering chamber 3, from the sputtering chamber 3 to the sputtering chamber 4, and the sputtering chamber 4 to the sputtering chamber 5, a plurality of stepped Ga concentration gradients are formed. Therefore, after the annealing treatment, Ga ions diffuse from the high concentration portion to the low concentration portion due to thermal diffusion, and the step gradient gradually becomes inconspicuous and eventually forms a linear distribution gradient.
  • a buffer layer is prepared on the absorption layer: by using a vacuum magnetron sputtering method, an In 2 Se 3 or ZnS alloy target is sputter deposited on the In 2 Se 3 or ZnS buffer layer, and the working pressure of the vacuum magnetron sputtering is 1 -5 X 10 - 3 Torr and Ar gas is introduced, and the temperature of the substrate is kept at room temperature.
  • the In 2 Se 3 or ZnS buffer layer is deposited to a thickness of 80 to 120 nm.
  • an intrinsic zinc oxide high-resistance layer is prepared on the buffer layer: the target is intrinsic zinc oxide (ZnO) by RF vacuum magnetron sputtering, and the working pressure of the RF vacuum magnetron sputtering is 1-5 X 10 — 3 Torr, operating frequency is 400K ⁇ 2MHz, and Ar gas is introduced, and the temperature of the substrate is kept at room temperature. 5 ⁇ The micron-thickness. Meter.
  • a low-impedance layer of indium tin oxide (In 2 0 3 : Sn0 2 ) film is prepared on the intrinsic zinc oxide high-resistance layer: the target is indium tin oxide (In 2 0 3 : by vacuum DC magnetron sputtering).
  • the mass ratio of Sn0 2 ), In 2 0 3 : Sn0 2 is 9 :1, and the working pressure of vacuum DC magnetron sputtering is 1_5 X 10 - 3 Torr, and Ar is doped with 2% to 5% 0 2 Gas, the temperature of the substrate is kept at room temperature.
  • the thickness of the layer is 0.3 to 0.3 ⁇ m.
  • A1 electrode was prepared by sputtering method using A1 target, and finally a copper indium gallium selenide thin film solar cell with a concentration gradient of Ga was obtained.
  • Figure 3 is a graph of secondary ion mass spectrometry (SIMS) analysis of a solar cell absorber layer prepared in accordance with the method of the present invention.
  • the concentration of Ga was highest on the side of the Mo back electrode, and then decreased toward the surface of the CIGS film, indicating a band gap having a gradient distribution.
  • the present invention has the following advantages: all the processes of the present invention are dry process processes, and the process does not use chemical solvents and solutions.
  • the absorption layer of the solar cell can be obtained in one step to obtain a stable crystalline absorption layer, eliminating the need for a process of selenization or vulcanization of the absorption layer, which greatly shortens the production cycle, reduces the production equipment, and avoids the production process. Environmental pollution and potential dangers.
  • the process steps of the present invention are simplified, energy consumption is small, and thus the production cost is reduced.

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Abstract

本发明涉及一种铜铟镓硒薄膜太阳能电池的制备方法，其包括：a）在衬底上制备钼背电极；b）在该钼背电极上制备铜铟镓硒吸收层，其中使用多个溅射腔进行分步溅射来完成制备吸收层；c）进行退火处理；d）在铜铟镓硒吸收层上制备In2Se3或ZnS缓冲层；e）在所述In2Se3或ZnS缓冲层上制备本征氧化锌高阻抗层；f）在所述本征氧化锌高阻抗层上制备氧化铟锡薄膜低阻抗层；g）在氧化铟锡薄膜低阻抗层上制备铝电极。

Description

一种铜铟镓硒薄膜太阳能电池的制备方法
技术领域：
本发明涉及太阳能电池领域， 更具体的， 涉及一种铜铟镓硒薄膜 太阳能电池的制备方法。
背景技术：
众所周知， 铜铟镓硒化合物具有黄铜矿结构， 可以制备在软性或 刚性的衬底上作为太阳能发电的材料，由此制成的铜铟镓硒薄膜太阳 能电池具有高稳定、低成本的优点。 目前地球上可利用的能源日趋短 少， 而石化能源在使用过程中会排放碳、硫的氧化物造成空气污染并 且加剧地球的温室效应， 使地球的环境恶化气候异常， 这已经是不争 的事实了。因此开发无污染的可再生能源是当前世界各国的首要科研 项目之一。而太阳能是无污染的能源，是可再生能源的最佳选择之一。 太阳能的开发利用首要的是开发可以产生将太阳能高效率转换成电 能的材料。
铜铟镓硒化合物材料是具有黄铜矿结构的化合物半导体材料，其 为直接带隙材料， 能吸收波长范围较大的太阳光， 且具有自调变自身 组成以形成 p-n结的特性，是公认的作为太阳能电池吸收层的最佳材 料之一， 例如铜铟镓二硒 （Cu (InGa) Se2)， 简称 CIGS, 为目前具有 最高光吸收能力的半导体材料。 由于 CIGS的高光吸收率优势， 使得 CIGS吸收层的厚度在 1~2μιη即可，以一般粗略估算，在量产制造时， CIGS材料的费用只需要 0. 03美元 /瓦， 因此极具竞争优势， 有望使 太阳能发电可以与传统的石化燃料发电成本相同甚至更低。因此如何 制备低成本、高效率的铜铟镓硒太阳能薄膜电池， 是目前最值得开发 研究的课题之一。
CIGS薄膜太阳能电池有两个优点： 1是光电转换层可以很薄， 为 几微米； 二是其带隙 (禁带宽度)可以通过 Ga (镓)在铜铟镓硒化合物 的比例含量来调控。 根据现有技术， Ga和 In的比例与带隙 (Eg) 存 在如下的关系， Eg (eV) =1. 02+ 0. 67y +0. l ly (y-l) , 其中 y=In/ (Ga + In) 的原子含量比例。 理论说明， 单一带隙的太阳能电池不能最大 限度的利用太阳能， 也就是光子能量太小的产生不了电子-空穴对， 能量太大的光子也只能激发一个电子-空穴对， 多余的能量只能转化 成不利于太阳能电池效率的热而已。因此从提高太阳电池效率的角度 考虑， 希望太阳能电池有很多的带隙以尽量吸收更多的太阳能， 而
CIGS 化合物的带隙的可调特性恰恰可以实现如此的设想。 在制备 CIGS薄膜时可以调节 Ga的含量比例。 增加 Ga的比例， CIGS化合物 的禁带带隙会升高。
现有文献中已记载制备 CIGS薄膜的方法主要有：（1)硒化法， (2) 叠层法， （3)多源 （二或三源）蒸发法， （4)溅射法， （5)沉积法， （6) 喷涂法， （7)旋涂法， （8)真空加热合成法等。 而这（1)硒化法， （2) 叠层法， （3)多源（二或三源）蒸发法， （4)溅射法皆在某个工艺流程 中需要对 CIGS薄膜进行硫化或硒化处理， 通过硫化或硒化处理可以 使 S、Se原子经扩散作用与 Cu-In-Ga进行反应以生成 CuInGaSe 化 合物， 此过程称为硫化或硒化。
硒化制备具有黄铜矿结构的薄膜太阳能电池的方法存在着一些 缺点例如生产周期长、 耗能多、 消耗 Se多、 Se 的蒸汽有剧毒及 Se 的分布不均匀， Se存在梯度等等。
另外对于调控 Ga的梯度分布工艺， 上述的各种工艺方法比较难 以一步到位的实现。例如美国的 NREL实验室开发的三阶段共蒸发法， 其实现 Ga呈上述的带隙梯度 A或 V字形带隙梯度是在三个阶段不同 的元素参与蒸发反应， 工艺非常复杂且需要实时控制精准方能实现。 此种方法虽然可以制备高转换效率的太阳能薄膜电池，但是不利于低 成本、 大面积、 规模化的生产。
发明内容
本发明提供一种铜铟镓硒薄膜太阳能电池的制备方法， 其包括: a) 在衬底上制备钼背电极；
b )采用多次分步溅射方法在该钼背电极上制备铜铟镓硒吸收层： 其中， 采用下述溅射设备来制备吸收层： 该溅射设备包括： 输入 平台、 输入腔、 N个溅射腔、 卸载腔， 卸载平台， 其中 N个溅射腔级 联串在一起， 输入腔的内部体积小于或等于溅射腔的内部体积， 卸载 腔的内部体积小于或等于溅射腔的内部体积；并且衬底从输入腔传送 至第一个溅射腔内时不破坏该第一个溅射腔的真空环境，和衬底从最 后一个溅射腔传送至该卸载腔时不破坏该最后一个溅射腔的真空环 境， 所述 N个溅射腔中的每一个溅射腔内都安装一个 CuInxGai—xSe2合 金靶， 以功率密度 2至 3W/cm2之间的任意功率密度对该合金靶溅射 1 至 2分钟， 每一个溅射腔内的工作压力均为 1X10— 4Torr， 腔内的衬 底温度保持在 200°C至 450°C之间的任意温度；
c) 进行退火处理： 在卸载腔内以快速加热方式对铜铟镓硒吸收 层进行退火处理，其温度为 400°C至 600°C，退火时间为 55至 90秒， 使得铜铟镓硒吸收层中的镓浓度形成梯度，其在该吸收层与钼背电极 接触的一侧的浓度最高， 在该吸收层的相对另一侧的浓度最低；
d) 在铜铟镓硒吸收层上制备 In2Se3或 ZnS缓冲层， 其厚度为 80 至 120纳米；
e) 在所述 In2Se3或 ZnS缓冲层上制备本征氧化锌高阻抗层， 其 厚度为 0.1至 0.5微米；
f) 在所述本征氧化锌高阻抗层上制备氧化铟锡薄膜低阻抗层， 其厚度为 0.3至 0.8微米；
g) 在氧化铟锡薄膜低阻抗层上制备铝电极。
其中： 所述铜铟镓硒吸收层的厚度为 1.5微米至 2微米。
其中： 在执行步骤 b) 中， 所述溅射腔的个数为 5个， 并且对于 第一溅射腔中的 CuInxGai—xSe2合金靶， x=0， 对于第二溅射腔中的 CuInxG -xSe2合金靶， 0.2〈x〈0.4， 对于第三溅射腔中的 CuInxG -xSe2 合金靶， 0.4〈x〈0.6， 对于第四溅射腔中的 CuInxG —xSe2合金靶， 0.6〈x〈0.7， 对于第五溅射腔中的 CuInxG -xSe2合金靶， x=0.7。
其中： 在执行步骤 d)中， 利用真空磁控溅射法， 采用 In2Se3 或 ZnS合金靶， 真空磁控溅射的工作压力为 1-5X10— 3 Torr 并通入 Ar 气体， 衬底的温度保持在室温。
其中： 在执行步骤 e) 中， 利用射频真空磁控溅射法， 靶材为本 征氧化锌， 射频真空磁控溅射的工作压力为 1-5X10— 3Torr， 工作频 率为 400K~2願 z， 并通入 Ar气体， 衬底的温度保持在室温。
其中： 在执行步骤 f) 中， 利用真空直流磁控溅射法， 靶材为氧 化铟锡 In203 : Sn02， ln203 : Sn02的质量比为 9： 1， 真空直流磁控溅射的 工作压力为 1-5 X 10— 3Torr，并通入掺有 2%至 5%02的 Ar气体，衬底的 温度保持室温。
其中： 所述溅射腔的个数为 2、 3、 4、 6、 7或者 8个。
其中： 所述镓浓度梯度为直线式分布。
根据本发明的方法，无硒化工艺流程及无镉的 In2Se3或 ZnS缓冲 层， 不但可以避免 H2Se、 H2S的有毒气体， 并且使用无镉的化合物， 既符合环保又可降低成本， 并且使得生产工艺设备简单能源消耗小， 生产周期短等优势。
本发明与现有技术相比有以下优点：本发明所有的工艺皆为干式 工艺流程， 工艺过程不使用化学溶剂与溶液。太阳能电池的吸收层制 备采用一步操作即可得到稳定结晶的吸收层，不再需要对吸收层进行 硒化或硫化的工业程序， 大大缩短了生产周期， 减少了生产设备， 也 避免了生产过程中的环境污染和潜在的危险。本发明的工艺步骤简化， 能源消耗小， 因此降低了生产成本。
附图说明
图 1 是本发明的制备铜铟镓硒薄膜太阳能电池吸收层的方法的 流程图；
图 2是本发明采用的制备吸收层的溅射设备结构示意图； 图 3 是对根据本发明的方法制备的太阳能电池吸收层所做的二 次离子质谱 (SIMS) 分析曲线图。
具体实施方式
图 1 是本发明的制备铜铟镓硒薄膜太阳能电池吸收层的方法的 流程图， 如图所示：
首先在衬底上制备背电极。所述衬底可以选择钠钙玻璃或者不锈 钢薄片，一般选用 l-3mm厚的钠钙玻璃或者 0. 2匪厚不锈钢薄片。采 用磁控溅射法沉积 0. 8微米厚的钼 （Mo) 金属作为背电极。
接着采用多次分步溅射方法在背电极上制备吸收层：本发明采用 一种特制的溅射设备来制备吸收层。
图 2是本发明采用的制备吸收层的溅射设备结构示意图。 如图 2 所示， 该溅射设备包括： 输入平台、 输入腔、 溅射腔 1、 溅射腔 2、 溅射腔 3、 溅射腔 4、 溅射腔 5、 卸载腔， 卸载平台， 另外还包括为 示出的传送机构，其用于将衬底一片一片地从输入平台依次进行传送， 最后到达卸载平台， 其中输入平台将衬底输送到输入腔后， 再由传送 机构送入到溅射腔 1。 在这里， 在溅射腔 1之前设置一个输入腔， 因 为其内部没有靶材等和 /或其它设置， 该腔内体积可以设计成较小， 通常会小于溅射腔的腔内体积， 但也可以等于溅射腔的腔内体积， 其 作用是完成衬底在被溅射之前所需要进行的温度处理（如加热）以及 真空预处理。衬底从输入腔传送至溅射腔 1不需要破坏溅射腔 1的真 空环境。设置输入腔作为缓冲腔的好处： 设置输入腔代替溅射腔常处 在大气环境下， 避免了溅射腔内的靶材接触到大气中的水气、 杂质、 粉尘等， 提高了工艺质量。
溅射腔 1内安装一个 CuInxG -xSe2合金靶 1，其中 x=0， 以功率密 度 2至 3W/cm2之间的任意功率密度对该靶 1溅射 1至 2分钟，接着将 该衬底传送至溅射腔 2， 溅射腔 2内安装一个 CuInxGai—xSe2合金靶 2， 其中 0. 2<x<0. 4， 以功率密度 2至 3W/cm2之间的任意功率密度对该靶 2溅射 1至 2分钟， 接着将该衬底传送至溅射腔 3， 溅射腔 3内安装 一个 CuInxG — xSe2合金靶 3， 其中 0. 4〈x〈0. 6， 功率密度 2至 3W/cm2 之间的任意功率密度对该靶 3溅射溅射 1至 2分钟，接着将该衬底传 送至溅射腔 4， 溅射腔 4 内安装一个 CuInxGai—xSe2合金靶 4， 其中 0. 6〈x〈0. 7， 以功率密度 2至 3W/cm2之间的任意功率密度对该靶 4溅 射 1至 2分钟， 接着将该衬底传送至溅射腔 5， 溅射腔 5内安装一个 CuInxG -xSe2合金靶 5， 其中 x=0. 7， 以功率密度 2至 3W/cm2之间的任 意功率密度对该靶 5溅射 1至 2分钟，最终在钼背电极上沉积铜铟镓 硒吸收层的厚度为 1. 5微米至 2微米。溅射腔 1-5内的工作压力为 1 X 10— 4Torr， 衬底的温度保持在 200°C至 450°C之间的任意温度。经溅 射后的衬底被传送到卸载腔， 使用卸载腔的原理与输入腔基本相同， 即衬底从溅射腔 5传送至卸载腔不需要破坏该溅射腔 5的真空环境， 并且还可以在卸载腔内完成退火或其它的温度处理。卸载腔的内部体 积小于或等于溅射腔的内部体积。之后衬底再被传送至卸载平台， 将 制备完吸收层的衬底收集到衬底花篮里。
本发明在这里虽然公开了 5个溅射腔作为例子进行说明，但是本 领域的技术人员都知道， 可以根据实际需要， 使用 2-4个溅射腔， 甚 至还可以使用多于 5个溅射腔， 例如、 6个、 7个、 8个或以上等。 当采用溅射腔的个数不同， 和 /或沉积铜铟镓硒吸收层的厚度不同， CuInxG -xSe2合金靶中的 x的取值也相应的不同， 这是本领域的技术 人员都想得到的。
随后进行退火处理： 对卸载腔抽真空， 在卸载腔内以快速加热方 式对铜铟镓硒吸收层进行退火处理， 其温度为 40CTC至 600°C， 退火 时间为 55至 90秒。在退火过程中不需要通入任何气体。在退火过程 中， 由于 Ga离子会从浓度高的部分向浓度低的部分热扩散， 使得铜 铟镓硒吸收层中的 Ga浓度形成梯度，其在该吸收层与 Mo背电极接触 的一侧的浓度最高， 在该吸收层的相对另一侧的浓度最低。经过退火 处理的铜铟镓硒吸收层具有黄铜矿结构，并通过热能进行局部离子扩 散， 提高结晶状态， 提高太阳能电池主吸收层的光伏发电效率。
这里再详细说明一下本发明实施的退火工艺。从溅射腔 1至溅射 腔 5 对合金靶材进行溅射的过程中， 当衬底从溅射腔 1传送至溅射 腔 2并溅射完成时， Ga浓度在衬底内部形成阶梯式的梯度， 接着从 溅射腔 2到溅射腔 3、 从溅射腔 3到溅射腔 4、 以及溅射腔 4到溅射 腔 5之后， 形成多个阶梯式的 Ga浓度梯度。 因此， 经过退火处理之 后， 由于热扩散作用， Ga 离子会从浓度高的部分向浓度低的部分扩 散， 阶梯式梯度逐渐不明显并最终形成直线式分布的梯度。
再接着在吸收层上制备缓冲层： 利用真空磁控溅射法， 采用 In2Se3 或 ZnS合金靶， 溅射沉积 In2Se3或 ZnS缓冲层， 真空磁控溅 射的工作压力为 1-5 X 10— 3Torr 并通入 Ar气体， 衬底的温度保持在 室温。 所述 In2Se3 或 ZnS缓冲层的沉积厚度为 80至 120纳米。
再接着在缓冲层上制备本征氧化锌高阻抗层：利用射频真空磁控 溅射法， 靶材为本征氧化锌（ZnO), 射频真空磁控溅射的工作压力为 1-5 X 10— 3 Torr, 工作频率为 400K~2MHz， 并通入 Ar气体， 衬底的温 度保持在室温。所述本征氧化锌高阻抗层的沉积厚度为 0. 1至 0. 5微 米。
再接着在本征氧化锌高阻抗层上制备氧化铟锡 （In203 : Sn02) 薄 膜低阻抗层：利用真空直流磁控溅射法，靶材为氧化铟锡（In203 : Sn02)， In203: Sn02的质量比为 9 : 1，真空直流磁控溅射的工作压力为 1_5 X 10— 3 Torr, 并通入掺有 2%至 5% 02 的 Ar气体， 衬底的温度保持室温。 所 述氧化铟锡薄膜低阻抗层的沉积厚度为 0. 3至 0. 8微米。
最后在氧化铟锡薄膜低阻抗层上制备铝电极： 利用 A1靶材， 通 过溅射法制备 A1电极，最终得到具有 Ga的浓度梯度的铜铟镓硒薄膜 太阳能电池。
图 3 是对根据本发明的方法制备的太阳能电池吸收层所做的二 次离子质谱 (SIMS) 分析曲线图。 Ga的浓度在 Mo背电极侧最高， 然 后到 CIGS薄膜表面递减， 表明具有梯度分布的禁带宽度。
本发明与现有技术相比有以下优点：本发明所有的工艺皆为干式 工艺流程， 工艺过程不使用化学溶剂与溶液。太阳能电池的吸收层制 备采用一步操作即可得到稳定结晶的吸收层，不再需要对吸收层进行 硒化或硫化的工艺程序， 大大缩短了生产周期， 减少了生产设备， 也 避免了生产过程中的环境污染和潜在的危险。本发明的工艺步骤简化， 能源消耗小， 因此降低了生产成本。

Claims

权利要求书
1. 一种铜铟镓硒薄膜太阳能电池的制备方法， 其包括： a) 在衬底上制备钼背电极；
b )采用多次分步溅射方法在该钼背电极上制备铜铟镓硒吸收层： 其中， 采用下述溅射设备来制备吸收层： 该溅射设备包括： 输入 平台、 输入腔、 N个溅射腔、 卸载腔， 卸载平台， 其中 N个溅射腔级 联串在一起， 输入腔的内部体积小于或等于溅射腔的内部体积， 卸载 腔的内部体积小于或等于溅射腔的内部体积；并且衬底从输入腔传送 至第一个溅射腔内时不破坏该第一个溅射腔的真空环境，和衬底从最 后一个溅射腔传送至该卸载腔时不破坏该最后一个溅射腔的真空环 境， 所述 N个溅射腔中的每一个溅射腔内都安装一个 CuInxGai—xSe2合 金靶， 以功率密度 2至 3W/cm2之间的任意功率密度对该合金靶溅射 1 至 2分钟， 每一个溅射腔内的工作压力均为 1 X 10— 4Torr， 腔内的衬 底温度保持在 200°C至 450°C之间的任意温度；
c ) 进行退火处理： 在卸载腔内以快速加热方式对铜铟镓硒吸收 层进行退火处理，其温度为 400°C至 600°C，退火时间为 55至 90秒， 使得铜铟镓硒吸收层中的镓浓度形成梯度，其在该吸收层与钼背电极 接触的一侧的浓度最高， 在该吸收层的相对另一侧的浓度最低；
d) 在铜铟镓硒吸收层上制备 In2Se3或 ZnS缓冲层， 其厚度为 80 至 120纳米；
e ) 在所述 In2Se3或 ZnS缓冲层上制备本征氧化锌高阻抗层， 其 厚度为 0. 1至 0. 5微米；
f ) 在所述本征氧化锌高阻抗层上制备氧化铟锡薄膜低阻抗层， 其厚度为 0. 3至 0. 8微米；
g) 在氧化铟锡薄膜低阻抗层上制备铝电极。
2. 如权利要求 1所述的制备方法， 其特征在于： 所述铜铟镓硒 吸收层的厚度为 1. 5微米至 2微米。
3. 如权利要求 1所述的制备方法， 其特征在于：在执行步骤 b ) 中，所述溅射腔的个数为 5个，并且对于第一溅射腔中的 CuInxG -xSe2 合金靶， x=0，对于第二溅射腔中的 CuInxG -xSe2合金靶，0. 2<x<0. 4， 对于第三溅射腔中的 CuInxGai—xSe2合金靶， 0.4〈x〈0.6，对于第四溅射 腔中的 CuInxGai—xSe2合金靶， 0.6〈x〈0.7， 对于第五溅射腔中的 CuInxG — xSe2合金靶， x=0.7。
4. 如权利要求 1所述的制备方法， 其特征在于：在执行步骤 d) 中， 利用真空磁控溅射法， 采用 In2Se3 或 ZnS合金靶， 真空磁控溅 射的工作压力为 1-5X10— 3 Torr 并通入 Ar气体， 衬底的温度保持在 至温。
5. 如权利要求 1所述的制备方法， 其特征在于：在执行步骤 e) 中， 利用射频真空磁控溅射法， 靶材为本征氧化锌， 射频真空磁控溅 射的工作压力为 1-5X10— 3Torr， 工作频率为 400K~2MHz， 并通入 Ar 气体， 衬底的温度保持在室温。
6. 如权利要求 1所述的制备方法， 其特征在于：在执行步骤 f) 中，利用真空直流磁控溅射法，靶材为氧化铟锡 In203:Sn02， In203:Sn02 的质量比为 9:1， 真空直流磁控溅射的工作压力为 1-5X10— 3Torr， 并 通入掺有 2%至 5%02的 Ar气体， 衬底的温度保持室温。
7. 如权利要求 1所述的制备方法， 其特征在于： 所述溅射腔的 个数为 2、 3、 4、 6、 7或者 8个。
8. 如权利要求 1所述的制备方法， 其特征在于： 所述镓浓度梯 度为直线式分布。
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