WO2011107035A1

WO2011107035A1 - Method for preparing copper-indium-gallium-selenium film for solar cell photo-absorption layer by magnetron sputtering process

Info

Publication number: WO2011107035A1
Application number: PCT/CN2011/071558
Authority: WO
Inventors: 黄富强; 王耀明; 朱小龙; 李爱民; 张雷
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2010-03-05
Filing date: 2011-03-07
Publication date: 2011-09-09
Anticipated expiration: 2012-09-05
Also published as: CN101768729A; CN101768729B

Abstract

Disclosed is a method for preparing copper-indium-gallium-selenium (CIGS) film for photo-absorption layer of solar cell, which comprises the steps of preparing a CIGS precursor film (200) by magnetron sputtering on a bottom electrode (101) using single target sputtering, or simultaneous or alternate sputtering of Cu-rich target and Cu-deficiency target, wherein the film has high reactive activity and can be reactively sintered quickly; and carrying out a heat treatment for the CIGS precursor film (200) to quickly react to produce a CIGS film for photo-absorption layer of solar cell which is even, compact, uniform and good at photoelectric property.

Description

磁控溅射法制备铜铟镓硒薄膜太阳电池光吸收层的方法技术领域 Method for preparing copper indium gallium selenide thin film solar cell light absorbing layer by magnetron sputtering

本发明涉及铜铟镓硒 (CIGS)薄膜太阳电池光吸收层的制备方法，更确切地说采用磁控溅射法制备 CIGS前驱薄膜，然后进行热处理制成太阳电池光吸收层，属于光伏材料新能源技术领域。背景技术 The invention relates to a method for preparing a light absorption layer of a copper indium gallium selenide (CIGS) thin film solar cell, more precisely, a magnetron sputtering method for preparing a CIGS precursor film, and then performing heat treatment to form a solar cell light absorbing layer, which belongs to a new photovoltaic material. The field of energy technology. Background technique

铜铟镓硒 (Cu(I_n,G_a)Se₂，简称 CIGS)薄膜太阳电池是新一代最有前途的太阳电池，它具有成本低、效率高、寿命长、弱光性能好、抗辐射能力强、可柔性且环境友好等多方面的优点。自 20世纪 90年代以来， CIGS在所有薄膜太阳电池中，就一直是实验室转换效率最高的薄膜太阳电池。 2008年 4月，美国可再生能源实验室 (NREL) 又将其实验室最高转换效率刷新为 19.9%(Ingrid Repins, Miguel A. Contreras, Brian Egaas, Clay DeHart, John Scharf, Craig L. Perkins, Bobby To and Rommel Noufi, Progress in Photovoltaics: Research and Applications, 16(3), 235- 239, 2008) , 与多晶娃的实验室最高转换效率 20.3%已非常接近，发展前景巨大。 Copper indium gallium selenide (Cu(I _n ,G _a )Se ₂ , referred to as CIGS) thin film solar cell is the new generation of the most promising solar cell, which has low cost, high efficiency, long life, good low light performance and radiation resistance. The advantages of being strong, flexible and environmentally friendly. Since the 1990s, CIGS has been the most efficient thin film solar cell in the laboratory for all thin film solar cells. In April 2008, the US Renewable Energy Laboratory (NREL) updated its laboratory's maximum conversion efficiency to 19.9% (Ingrid Repins, Miguel A. Contreras, Brian Egaas, Clay DeHart, John Scharf, Craig L. Perkins, Bobby To and Rommel Noufi, Progress in Photovoltaics: Research and Applications, 16(3), 235-239, 2008), the highest conversion efficiency of 20.3% in the laboratory of polycrystalline silicon is very close, and the development prospect is huge.

CIGS光吸收层的制备是 CIGS薄膜太阳电池的核心工艺。目前产业界制备 CIGS 光吸收层的主要工艺包括蒸发法、磁控溅射 Cu-In-Ga预制膜后硒化法和蒸发-溅射杂化法等。但这些方法都不可避免地在薄膜的制备过程中会出现易挥发的中间相 (如 In₂Se、 In₄Se₃ InSe和 In₆Se₇等)，使薄膜最终的实际成分与名义成分差别很大；而且由于易挥发中间相的生成和挥发速度与温度、气压、挥发性物质的分压和表面气流状态等因素都密切相关，大面积温场中不可控因素 (分压、气流状态等)的涨落，会导致大面积薄膜成分出现不可控的变化，从而导致薄膜的均匀性和重复性都难以控制，电池的生产良率无法得到保证，严重制约了产业化生产的大规模扩张。发明内容 The preparation of the CIGS light absorbing layer is the core process of the CIGS thin film solar cell. At present, the main processes for preparing the CIGS light absorbing layer in the industry include evaporation method, magnetron sputtering Cu-In-Ga pre-fabrication film selenization method and evaporation-sputter hybridization method. However, these methods inevitably produce a volatile intermediate phase (such as In ₂ Se, In ₄ Se ₃ InSe, In ₆ Se _{7 ,} etc.) during the preparation of the film, so that the final actual composition of the film differs from the nominal composition. Large; and because the formation and volatilization rate of the volatile intermediate phase are closely related to temperature, pressure, partial pressure of volatile matter and surface gas flow state, uncontrollable factors (partial pressure, gas flow state, etc.) in large-area temperature field The fluctuation of the film will lead to uncontrollable changes in the film composition of the large area, which makes the film uniformity and repeatability difficult to control, and the production yield of the battery cannot be guaranteed, which seriously restricts the large-scale expansion of industrial production. Summary of the invention

本发明的目的在于提供 CIGS薄膜太阳电池光吸收层的一种制备方法，采用所述的方法可以提高大面积 CIGS薄膜制备工艺的稳定性和成分的均匀性，提高 CIGS薄膜太阳电池的光电转换效率和电池生产良率。本发明所提供的方法具有工艺可控性强，制备的薄膜质量高、均匀性好，工艺简单，适合工业化生产的特点。 The object of the present invention is to provide a preparation method of a light absorption layer of a CIGS thin film solar cell, which can improve the stability and composition uniformity of a large-area CIGS film preparation process, and improve the photoelectric conversion efficiency of a CIGS thin film solar cell. And battery production yield. The method provided by the invention has the advantages of strong controllability of the process, high quality of the film, good uniformity, simple process and suitable for industrial production.

因为， In₂Se、 In₄Se₃、 InSe和 In₆Se₇等物质在 300 °C以上都具有很高的蒸汽压，在 300°C以上这些物质都具有很强的挥发性，而已报道的 CIGS薄膜的制备温度往往在 500 °C以上 (Marianna Kemell, Mikko Ritala, and Markku Leskel, Critical Reviews in Solid State and Materials Sciences, 30: 1-31, 2005)。若在 CIGS薄膜的制备过程中生成这些高挥发性的中间物质，往往会导致 CIGS薄膜的最终成分难以控制。 Because substances such as In ₂ Se, In ₄ Se ₃ , InSe and In ₆ Se ₇ have a high vapor pressure above 300 °C, These materials are highly volatile above 300 ° C, and the reported CIGS films are often prepared at temperatures above 500 ° C (Marianna Kemell, Mikko Ritala, and Markku Leskel, Critical Reviews in Solid State and Materials Sciences, 30: 1-31, 2005). If these highly volatile intermediates are formed during the preparation of CIGS films, the final composition of the CIGS film is often difficult to control.

本发明通过磁控溅射法，采用化合物靶材在室温下制备出 CIGS前驱薄膜，这一方面避免了高温衬底导致的铟硒化合物的挥发问题；另一方面，在 CIGS前驱薄膜中，各元素之间紧密接触，处于原位复合的状态，在热处理反应时，物质输运路径非常短，反应速度非常快，快速生成蒸汽压非常低的铜铟镓硒多元化合物，有效地避免了元素的挥发；同时，由于常温制备， CIGS前驱薄膜处于高反应活性的热力学亚稳定状态，在热处理时，迅速生成大晶粒的高质量、高结晶 CIGS薄膜，十分有利于提高 CIGS薄膜太阳电池的光电转换效率。 The invention adopts a magnetron sputtering method to prepare a CIGS precursor film at room temperature by using a compound target, thereby avoiding the problem of volatilization of indium selenium compounds caused by a high temperature substrate; on the other hand, in the CIGS precursor film, each The elements are in close contact with each other and are in an in-situ composite state. During the heat treatment reaction, the material transport path is very short, the reaction speed is very fast, and the copper indium gallium selenide multi-component compound with very low vapor pressure is rapidly formed, effectively avoiding the elements. At the same time, due to the preparation at room temperature, the CIGS precursor film is in a highly reactive thermodynamic metastable state. When heat treatment, it rapidly forms large-grain, high-quality, high-crystalline CIGS film, which is very beneficial to improve the photoelectric conversion of CIGS thin film solar cells. effectiveness.

更具体地，本发明通过磁控溅射法，采用富铜靶和富铟靶在室温下制备出 CIGS 前驱薄膜，这一方面避免了高温衬底导致的铟硒化合物的挥发问题；另一方面，在 CIGS 前驱薄膜中，富铟相和富铜相紧密结合，处于原位复合的状态，在热处理反应时，物质输运路径非常短，反应速度非常快，快速生成蒸汽压非常低的铜铟镓硒多元化合物，有效地避免了元素的挥发。 More specifically, the present invention prepares a CIGS precursor film by a magnetron sputtering method using a copper-rich target and an indium-rich target at room temperature, thereby avoiding the problem of volatilization of the indium selenium compound caused by the high temperature substrate; In the CIGS precursor film, the indium-rich phase and the copper-rich phase are tightly combined and in-situ composite state. During the heat treatment reaction, the material transport path is very short, the reaction rate is very fast, and the copper indium with very low vapor pressure is rapidly formed. The gallium selenium multi-component compound effectively avoids the volatilization of the element.

实现本发明所提供的 CIGS薄膜太阳电池光吸收层制备方法的一种方案 (a)为： One solution (a) for realizing the preparation method of the CIGS thin film solar cell light absorbing layer provided by the present invention is:

CIGS薄膜太阳电池光吸收层的一种制备方法，其特征在于：采用包括射频溅射和直流溅射的磁控溅射法制备具有高反应活性的 CIGS前驱薄膜，并进行热处理以快速反应，制备 CIGS薄膜。具体包括以下工艺步骤： A preparation method of a light absorption layer of a CIGS thin film solar cell, characterized in that: a CIGS precursor film having high reactivity is prepared by magnetron sputtering including radio frequency sputtering and direct current sputtering, and heat treatment is performed to rapidly react and prepare CIGS film. Specifically, the following process steps are included:

(1)制备 CIGS前驱薄膜：在底电极 (101)上通过磁控溅射法，采用单靶溅射、或富铜靶和贫铜靶同时溅射，制备出 CIGS前驱薄膜 (200); (1) preparing a CIGS precursor film: a CIGS precursor film (200) is prepared by magnetron sputtering on a bottom electrode (101) by single target sputtering, or a copper-rich target and a copper-deficient target simultaneously sputtering;

(2) CIGS前驱薄膜热处理：在真空中或一定气压的惰性气氛中，将固态单质 Se源加热到 180°C〜450°C，形成 Se的饱和蒸汽压，将上述 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 10°C/min〜100°C/min的升温速度快速升温到 450°C〜600°C，并保温 10 min 〜60min，生成 CIGS薄膜太阳电池的光吸收层。 (2) Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C ~ 450 ° C in a vacuum or a certain pressure of inert atmosphere to form a saturated vapor pressure of Se, and the above CIGS precursor film is placed in a saturated Se In the vapor pressure, the temperature is rapidly raised to 450 ° C to 600 ° C at a temperature rising rate of 10 ° C / min to 100 ° C / min, and held for 10 min to 60 min to form a light absorbing layer of a CIGS thin film solar cell.

实现本发明所提供的 CIGS薄膜太阳电池光吸收层制备方法的另一种方案 (b)为： Another solution (b) for realizing the preparation method of the CIGS thin film solar cell light absorbing layer provided by the present invention is:

CIGS薄膜太阳电池光吸收层的一种制备方法，其特征在于包括以下步骤： A preparation method of a light absorption layer of a CIGS thin film solar cell, comprising the following steps:

(1)制备 CIGS前驱薄膜：在底电极 (101)上通过磁控溅射法，采用富铜靶和贫铜靶先后溅射，形成富铜层和贫铜层交替出现的叠层结构 (201〜20n)，制备出 CIGS前驱薄膜； (2)CIGS前驱薄膜热处理：在真空中或一定气压的惰性气氛中，将固态单质 Se源加热到 180°C〜450°C，形成 Se的饱和蒸汽压，将上述 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 10°C/min〜100°C/min的升温速度快速升温到 450°C〜600°C，并保温 10 min 〜60min，生成 CIGS薄膜太阳电池的光吸收层。 (1) Preparation of CIGS precursor film: On the bottom electrode (101), a copper-rich target and a copper-deficient target are successively sputtered by a magnetron sputtering method to form a laminated structure in which a copper-rich layer and a copper-depleted layer alternately appear (201). ~20n), preparing a CIGS precursor film; (2) Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C ~ 450 ° C in a vacuum or a certain pressure of inert atmosphere to form a saturated vapor pressure of Se, and the above CIGS precursor film is placed in a saturated Se In the vapor pressure, the temperature is rapidly raised to 450 ° C to 600 ° C at a temperature rising rate of 10 ° C / min to 100 ° C / min, and held for 10 min to 60 min to form a light absorbing layer of a CIGS thin film solar cell.

上述方案 (a)的制备步骤 (1)中，其中单靶溅射的靶材为 C_Ul__x(In, Ga)Se_2-x/2 (0.05 ^x 0.50)。 In the preparation step (1) of the above scheme (a), the single-target sputtering target is C _Ul _ _x (In, Ga) Se _2-x/2 (0.05 ^ x 0.50).

上述方案 ( )和方案 Cb)的制备步骤 (I)中，其中富铜靶为 Cu、CuSe、Cu₂Se和 Cu_1+xCIn, Ga)Se_2+x/2 (0.1 x 1.0)中的一种或几种的混合。 In the preparation step (I) of the above scheme ( ) and scheme Cb), wherein the copper-rich target is Cu, CuSe, Cu ₂ Se, and Cu _1+x CIn, Ga)Se _2+x/2 (0.1 x 1.0) One or a mixture of several.

上述方案 (a)和方案 (b)的制备步骤 (1)中，其中贫铜靶为 (In, Ga)₄Se₃、 (In, Ga)₂Se₃ Cu(In, Ga)₅Se₈、Cu(In, Ga)₃Se₅、 Cu₂(In, Ga)₄Se₇、 Cu₃(In, Ga)₅Se₉禾口 Cu_1-x(In, Ga)Se_2-x/2 (0.4 ^x< 1.0) 中的一种或几种的混合。 In the preparation step (1) of the above schemes (a) and (b), wherein the copper-deficient target is (In, Ga) ₄ Se ₃ , (In, Ga) ₂ Se ₃ Cu(In, Ga) ₅ Se ₈ , Cu(In, Ga) ₃ Se ₅ , Cu ₂ (In, Ga) ₄ Se ₇ , Cu ₃ (In, Ga) ₅ Se ₉ and Cu _1-x (In, Ga) Se _2-x/2 (0.4 A mixture of one or several of ^x< 1.0).

上述方案 (a)的制备步骤 (1)中，其中单靶的溅射条件为：采用射频溅射，溅射功率密度为 0.2W cm_²〜10W cm"², 靶距为 4 cm〜20 cm, 工作气压为 0.05Pa〜20Pa; 其中溅射功率密度优选为 0.5W cm_²〜5 W cm"²,靶距优选为 5 cm〜15 cm, 工作气压优选为 0.2Pa〜10Pa。 In the preparation step (1) of the above scheme (a), the sputtering condition of the single target is: by radio frequency sputtering, the sputtering power density is 0.2 W cm ^{2 2 to} 10 W cm" ² , and the target distance is 4 cm to 20 cm. The working gas pressure is 0.05 Pa to 20 Pa; wherein the sputtering power density is preferably 0.5 W cm ^{2 2 to} 5 W cm ^{2 2} , the target distance is preferably 5 cm to 15 cm, and the working gas pressure is preferably 0.2 Pa to 10 Pa.

上述方案 (a)和方案 (b)的制备步骤 (1)中，其中富铜靶的溅射条件为：采用直流溅射或射频溅射，溅射功率密度为 0.2W cm_²〜10W cm"², 靶距为 4 cm〜20 cm, 工作气压为 0.05Pa〜20Pa; 其中溅射功率密度优选为 0.5W cm_²〜5 W cm"², 靶距优选为 5 cm〜 15 cm, 工作气压优选为 0.2Pa〜10Pa。 In the preparation step (1) of the above schemes (a) and (b), wherein the sputtering condition of the copper-rich target is: by DC sputtering or radio frequency sputtering, the sputtering power density is 0.2 W cm ^{2 2 to} 10 W cm" ² , the target distance is 4 cm~20 cm, the working pressure is 0.05Pa~20Pa; wherein the sputtering power density is preferably 0.5W cm_ ² 〜5 W cm" ² , the target distance is preferably 5 cm~ 15 cm, and the working pressure is preferably It is 0.2Pa~10Pa.

上述方案 (a)和方案 (b)的制备步骤 (1)中，其中贫铜靶的溅射条件为：采用射频溅射，溅射功率密度为 0.2W cm_²〜10W cm"²,靶距为 4 cm〜20 cm,工作气压为 0.05Pa〜20Pa ；其中溅射功率密度优选为 0.5W cm_²〜5 W cm"², 靶距优选为 5 cm〜15 cm, 工作气压优选为 0.2Pa〜10Pa。 In the preparation step (1) of the above schemes (a) and (b), the sputtering condition of the copper-deficient target is: by radio frequency sputtering, the sputtering power density is 0.2 W cm_ ² 〜 10 W cm" ² , the target distance The working pressure is from 0.05 cm to 20 Pa, and the sputtering power density is preferably 0.5 W cm ^{2 2 to} 5 W cm ^{2 2} , the target distance is preferably 5 cm to 15 cm, and the working gas pressure is preferably 0.2 Pa. 10Pa.

上述方案 (b)的制备步骤 (1)中，其中富铜层和贫铜层的总层数为 2〜12层，优选为 3〜6层。 In the preparation step (1) of the above scheme (b), the total number of layers of the copper-rich layer and the copper-depleted layer is 2 to 12 layers, preferably 3 to 6 layers.

上述方案 (b)的制备步骤 (1)中，其中富铜层和贫铜层的单层厚度为 10nm〜1500nm，优选为 50nm〜1000nm。 In the preparation step (1) of the above scheme (b), the single layer thickness of the copper-rich layer and the copper-depleted layer is from 10 nm to 1500 nm, preferably from 50 nm to 1000 nm.

上述方案 (a)和方案 (b)的制备步骤 (1)中，其中 CIGS前驱薄膜中 Cu原子数与 In和 Ga原子数之和的比为 0.5〜1.0， S卩 0.5 Cu/(In+Ga) 1.0，优选为 0.5 Cu/(In+Ga)< 1.0，更优选为 0.7 Cu/(In+Ga) 0.95。 In the preparation step (1) of the above schemes (a) and (b), wherein the ratio of the number of Cu atoms to the sum of the numbers of In and Ga atoms in the CIGS precursor film is 0.5 to 1.0, S 卩 0.5 Cu / (In + Ga 1.0, preferably 0.5 Cu / (In + Ga) < 1.0, more preferably 0.7 Cu / (In + Ga) 0.95.

上述方案 (a)和方案 (b)的制备步骤 (1)中，其中 CIGS前驱薄膜中 Ga原子数与 In和 Ga原子数之和的比为 0〜1.0， S卩 0 Ga/(In+Ga) 1.0，优选为 0<Ga/(In+Ga)< 1.0，更优选为 0.2 Ga/(In+Ga) 0.4。 In the preparation step (1) of the above scheme (a) and scheme (b), wherein the number of Ga atoms and the In sum in the CIGS precursor film The ratio of the sum of the number of Ga atoms is 0 to 1.0, S 卩 0 Ga / (In + Ga) 1.0, preferably 0 < Ga / (In + Ga) < 1.0, more preferably 0.2 Ga / (In + Ga) 0.4 .

上述方案 (a)和方案 (b)的制备步骤 (1)中，其中 CIGS前驱薄膜的厚度为 500 nm〜 3500 nm, 优选为 1000 nm~2500 mn。 In the preparation step (1) of the above schemes (a) and (b), the thickness of the CIGS precursor film is 500 nm to 3500 nm, preferably 1000 nm to 2500 mn.

上述方案 (a)和方案 (b)的制备步骤 (2)中，其中的真空是指反应容器中的气压 2 Pa 上述方案 (a)和方案 (b)的制备步骤 (2)中，其中所述的惰性气氛为氮气、氦气、氖气、氩气中的一种或几种的混合，所述的一定气压为 5Pa〜100000Pa。本发明所提供的 CIGS薄膜的制备方法，简言之，首先采用常温磁控溅射法制备出高反应活性的 CIGS前驱薄膜，然后在 Se的气氛下进行热处理，制备出大晶粒的高结晶性 CIGS光吸收层薄膜。薄膜质量高，均匀性好，工艺简单，适合工业化生产。附图概述 In the preparation step (2) of the above schemes (a) and (b), the vacuum therein refers to the gas pressure in the reaction vessel 2 Pa in the preparation scheme (2) of the above scheme (a) and scheme (b), wherein The inert atmosphere is a mixture of one or more of nitrogen, helium, neon, and argon, and the predetermined gas pressure is 5 Pa to 100,000 Pa. The preparation method of the CIGS film provided by the invention is, in short, firstly, a high-reactivity CIGS precursor film is prepared by a normal temperature magnetron sputtering method, and then heat treatment is performed in a Se atmosphere to prepare a large crystallite high crystal. A CIGS light absorbing layer film. The film has high quality, good uniformity and simple process, which is suitable for industrial production. BRIEF abstract

图 1为本发明方案 (a)所制备的 CIGS前驱薄膜截面示意图； 1 is a schematic cross-sectional view of a CIGS precursor film prepared according to the embodiment (a) of the present invention;

图 2为本发明方案 (b)所制备的 CIGS前驱薄膜截面示意图； 2 is a schematic cross-sectional view of a CIGS precursor film prepared according to the embodiment (b) of the present invention;

图 3为实施例 13所制备的 CIGS薄膜的扫描电子显微镜 (SEM)图； Figure 3 is a scanning electron microscope (SEM) image of the CIGS film prepared in Example 13;

图 4 为实施例 17所制备的 CIGS薄膜太阳电池的 J-V曲线图。 4 is a J-V graph of a CIGS thin film solar cell prepared in Example 17.

图中，横坐标为电压 (voltage), 纵坐标为电流密度 (current density)和功率密度 (power density)。本发明的最佳实施方案 In the figure, the abscissa is voltage and the ordinate is current density and power density. BEST MODE FOR CARRYING OUT THE INVENTION

本发明所述的磁控溅射是指：在低压（一般指 0.01 Pa〜100 Pa) 的惰性气体（包括 He、 Ne、 Ar、 Kr、 H₂、 N₂等）下，通过电场的作用，使得惰性气体电离，形成惰性气体等离子体，轰击阴极材料，被溅出的阴极材料原子或分子沉积在基片上形成薄膜，这种技术为本发明所述的磁控溅射技术。其中直流磁控溅射是指电场由直流电提供，射频磁控溅射是指电场由射频交变电提供。 The magnetron sputtering according to the present invention means: under an inert gas (including He, Ne, Ar, Kr, H ₂ , N _{2 ,} etc.) at a low pressure (generally 0.01 Pa to 100 Pa), by the action of an electric field, The inert gas is ionized to form an inert gas plasma, bombarding the cathode material, and the deposited cathode material atoms or molecules are deposited on the substrate to form a thin film. This technique is the magnetron sputtering technique of the present invention. Among them, DC magnetron sputtering means that the electric field is supplied by direct current, and radio frequency magnetron sputtering means that the electric field is supplied by radio frequency alternating current.

本发明的技术构思及其优势如下： The technical idea of the present invention and its advantages are as follows:

本发明采用常温溅射法制备 CIGS前驱薄膜，无需加热，无需考虑 Se对溅射设备的腐蚀问题，显著简化了设备的设计和材料、加工的要求，大幅降低了设备成本，而且，由于成膜过程不需要预热一加热一冷却等耗时多的工艺步骤，加快了生产节拍，提高了生产效率，这对于降低电池的生产成本十分有利；并且，采用常温溅射法制备的 CIGS前驱薄膜，处于热力学亚稳定状态，反应活性高，通过热处理可快速生成大晶粒、高结晶、高质量的 CIGS光吸收层薄膜，十分有利于 CIGS薄膜太阳电池光电转换效率的提高。 The invention adopts the normal temperature sputtering method to prepare the CIGS precursor film without heating, and does not need to consider the corrosion problem of Se on the sputtering equipment, which simplifies the design of the equipment, the material and the processing requirements, greatly reduces the equipment cost, and, due to the film formation. The process does not require preheating, heating, cooling, and other time-consuming process steps, which speeds up the production cycle. The production efficiency is improved, which is very favorable for reducing the production cost of the battery; and the CIGS precursor film prepared by the normal temperature sputtering method is in a thermodynamic metastable state, has high reactivity, and can rapidly form large crystal grains and high crystals by heat treatment. The high quality CIGS light absorbing layer film is very beneficial to the improvement of photoelectric conversion efficiency of CIGS thin film solar cells.

本发明采用后期热处理，薄膜沉积与热处理分离，可实现热处理温度和气氛的精确控制，有利于大面积高质量 CIGS薄膜的制备，同时，前驱薄膜沉积与热处理的工艺节拍易于匹配，有利于加快生产速度，提高生产效率，从而降低生产成本。 The invention adopts post-heat treatment, film deposition and heat treatment separation, can realize precise control of heat treatment temperature and atmosphere, and is favorable for preparation of large-area high-quality CIGS film, and at the same time, the process tempo of precursor film deposition and heat treatment is easy to match, which is favorable for accelerating production. Speed, increase production efficiency, and thus reduce production costs.

本发明所提供的 CIGS薄膜制备方法，可采用不同组分的靶材沉积多层前驱膜，实现薄膜中元素浓度（如 Ga等）纵向梯度分布的精确控制，这不仅有利于最大限度地利用太阳光，同时可形成背场效应和良好 /^-«结界面，减少界面复合，提高电池的开路电压和填充因子，从而大幅提高电池的光电转换效率。 The method for preparing a CIGS film provided by the invention can deposit a multi-layer precursor film by using different target targets, thereby realizing precise control of the longitudinal gradient distribution of element concentration (such as Ga) in the film, which is not only beneficial to maximizing the use of the sun. Light, at the same time can form back-field effect and good / ^ - « junction interface, reduce interface recombination, improve the open circuit voltage and fill factor of the battery, thereby greatly improving the photoelectric conversion efficiency of the battery.

下面对照附图 1和附图 2详细说明本发明所述的制备方法及其优选方式。如图 1 和图 2所示，本发明所采用的基片可以是普通碱石灰玻璃、不锈钢箔、钛箔和聚酰亚胺膜等材料。基片上的底电极 101是钼电极，钼电极是采用磁控溅射法制备的。 The preparation method of the present invention and its preferred mode will be described in detail below with reference to Figs. 1 and 2. As shown in Figs. 1 and 2, the substrate used in the present invention may be a material such as ordinary soda lime glass, stainless steel foil, titanium foil, and polyimide film. The bottom electrode 101 on the substrate is a molybdenum electrode which is prepared by magnetron sputtering.

在底电极上的 CIGS光吸收层，本发明所提供的制备方法可以通过两种方案实现第一种方案如图 1所示。在底电极上 101通过常温磁控溅射法，采用 C_Ul__x(In, Ga)Se₂__x/2 (0.05 _x 0.50)化合物靶材进行单靶溅射，在常温下制备出 CIGS前驱薄膜 200，然后经过热处理生成 CIGS光吸收层；也可以采用富铜靶和贫铜靶同时溅射，在常温下 CIGS前驱薄膜 200，并经过热处理生成 CIGS光吸收层。对于富铜靶，如 Cu、 CuSe、 01₂86和01_1+!5( 0&)86_2+!5/2 (0.1 1.0)等，既可采用直流溅射，也可采用射频溅射；对于贫铜靶，如 (In, Ga)₄Se₃、（In, Ga)₂Se₃、 Cu(In, Ga)₅Se₈、 Cu(In, Ga)₃Se₅、 Cu₂(In, Ga)₄Se₇、 Cu₃(In, Ga)₅Se₉和 Cu_1-x(In, Ga)Se_2-x/2 (0.4 x< 1.0)等，由于靶材的电导率很差，采用直流溅射制膜时会形成电荷积累，导致溅射速率不稳定，甚至辉光自动熄灭，因而只能采用对靶材电导率不敏感的射频溅射；对于单靶溅射靶材 C_Ul__x(In, Ga)Se_2-x/2 (0.05 ^x^ 0.50), 其电导率也很低，同样也只能采用射频溅射。 The CIGS light absorbing layer on the bottom electrode, the preparation method provided by the present invention can realize the first scheme by two schemes as shown in FIG. On the bottom electrode 101, a single target sputtering was performed by a normal temperature magnetron sputtering method using a C _Ul _ _x (In, Ga) Se ₂ _ _x/2 (0.05 _x 0.50) compound target, and a CIGS precursor was prepared at normal temperature. The film 200 is then subjected to heat treatment to form a CIGS light absorbing layer. The copper-rich target and the copper-deficient target may also be simultaneously sputtered, and the CIGS precursor film 200 is heated at room temperature to form a CIGS light absorbing layer. For copper-rich targets, such as Cu, CuSe, 01 ₂ 86 and 01 _1+!5 ( 0& ) 86 _{2+! 5/2} (0.1 1.0), etc., either DC sputtering or RF sputtering; Copper-poor targets such as (In, Ga) ₄ Se ₃ , (In, Ga) ₂ Se ₃ , Cu(In, Ga) ₅ Se ₈ , Cu(In, Ga) ₃ Se ₅ , Cu ₂ (In, Ga) ₄ Se ₇ , Cu ₃ (In, Ga) ₅ Se ₉ and Cu _1-x (In, Ga) Se _2-x/2 (0.4 x < 1.0), etc., due to the poor conductivity of the target, using DC sputtering When the film is formed, charge accumulation occurs, resulting in unstable sputtering rate, and even the glow is automatically extinguished. Therefore, only RF sputtering which is insensitive to the target conductivity can be used; for the single target sputtering target C _Ul _ _x ( In, Ga)Se _2-x/2 (0.05 ^x^ 0.50), its conductivity is also very low, and it can only be used for RF sputtering.

一个典型的单靶溅射制备 CIGS光吸收层的制备流程为：以 C_U。.₈(In, Ga)S_ei.₉作为靶材，采用射频溅射法在常温下制备出 CIGS前驱薄膜，溅射功率密度为 2 W cm_²，靶距为 8 cm,工作气压为 0.8 Pa,所制备的 CIGS前驱薄膜的厚度为 1500 nm;在 10000 Pa 的氮气中，将 CIGS前驱薄膜置于 Se源温度为 250°C的 Se的饱和蒸汽压中，以 20°C/min 快速升温至 530°C并保温 30 min, 即制备出所需的 CIGS光吸收层。一个典型的富铜靶和贫铜靶同时溅射制备 CIGS光吸收层的制备流程为：以 Cu₂Se 靶作为富铜靶， Cu(In, 0&)₅8 靶作为贫铜靶； Cu₂Se靶采用直流溅射，溅射功率密度为 0.8 W cm"²,靶距为 8 cm,工作气压为 0.8 Pa;在常温下制备出 CIGS前驱薄膜， Cu(In, Ga)₅Se₈靶采用射频溅射，溅射功率密度为 2 W cm_²，靶距为 8 cm, 工作气压为 0.8 Pa ；所制备的 CIGS前驱薄膜的厚度为 1000 nm，薄膜中 Cu/(In+Ga)=0.90， Ga/(In+Ga)=0.30 ；在 30000 Pa的氮气中，将 CIGS前驱薄膜置于 Se源温度为 300°C的 Se的饱和蒸汽压中，以 30°C/min快速升温至 550°C并保温 20 min，即制备出所需的 CIGS光吸收层。 The preparation process of a typical single target sputtering preparation of CIGS light absorbing layer is as follows: C _U . ₈ (In, Ga)S _ei . ₉ as a target, a CIGS precursor film was prepared by RF sputtering at room temperature with a sputtering power density of 2 W cm_ ² , a target distance of 8 cm and a working pressure of 0.8 Pa. The thickness of the prepared CIGS precursor film is 1500 nm; in a nitrogen gas of 10000 Pa, the CIGS precursor film is placed in a saturated vapor pressure of Se at a Se source temperature of 250 ° C, and the temperature is rapidly raised to 20 ° C / min to The desired CIGS light absorbing layer was prepared by 530 ° C and holding for 30 min. The preparation process of a typical copper-rich target and a copper-poor target simultaneously sputtering to prepare a CIGS light absorbing layer is as follows: a Cu ₂ Se target is used as a copper-rich target, and a Cu(In, 0&) ₅ 8 target is used as a copper-deficient target; Cu ₂ Se The target is DC sputtering, the sputtering power density is 0.8 W cm" ² , the target distance is 8 cm, and the working pressure is 0.8 Pa. The CIGS precursor film is prepared at room temperature, and the Cu(In, Ga) ₅ Se ₈ target is RF. Sputtering, sputtering power density is 2 W cm_ ² , target distance is 8 cm, working pressure is 0.8 Pa; the thickness of the prepared CIGS precursor film is 1000 nm, Cu/(In+Ga)=0.90, Ga in the film /(In+Ga)=0.30 ; The CIGS precursor film was placed in a saturated vapor pressure of Se at a Se source temperature of 300 ° C in a nitrogen gas of 30,000 Pa, and rapidly heated to 550 ° C at 30 ° C / min and The desired CIGS light absorbing layer was prepared by holding for 20 minutes.

第二种方案如图 2所示。在底电极 101上通过常温磁控溅射法，采用富铜靶和贫铜靶先后溅射，形成富铜层和贫铜层交替出现的叠层结构（201〜20n) ，在常温下制备出 CIGS前驱薄膜，并经过热处理生成 CIGS光吸收层。其中最底层 201既可是富铜层也可是贫铜层；顶层 20η同样既可是富铜层也可是贫铜层，顶层 20η优选为贫铜层一个典型的富铜靶和贫铜靶先后溅射制备 CIGS光吸收层的制备流程为：以 Cu₂Se 靶作为富铜靶，（In, 0 ^ 靶作为贫铜靶； Cu₂Se靶采用射频溅射，溅射功率密度为 0.4 W cm"², 靶距为 8 cm，工作气压为 0.8 Pa; (In, Ga)₄Se₃靶也采用射频溅射，溅射功率密度为 2 W cm_²，靶距为 8 cm，工作气压为 0.8 Pa; 首先制备的底层 201层为贫铜的 (In, Ga)₄Se₃，然后制备富铜的第二次 202层 Cu₂Se，再次制备贫铜的顶层 203层 (In, Ga)₄Se₃，形成 1500 nm厚的 CIGS前驱薄膜，薄膜中 Cu/(In+Ga)=0.85， Ga/(In+Ga)=0.30 ；在 50 Pa的氮气中，将前驱薄膜置于 Se源温度为 250°C的 Se的饱和蒸汽压中，以 30°C/min快速升温至 550°C并保温 20 min, 即制备出所需的 CIGS光吸收层。 The second scheme is shown in Figure 2. On the bottom electrode 101, a copper-rich target and a copper-deficient target are successively sputtered by a normal temperature magnetron sputtering method to form a laminated structure (201 to 20n) in which a copper-rich layer and a copper-depleted layer alternately appear, and are prepared at normal temperature. The CIGS precursor film is heat treated to form a CIGS light absorbing layer. The bottom layer 201 may be either a copper-rich layer or a copper-depleted layer; the top layer 20n may also be a copper-rich layer or a copper-depleted layer, and the top layer 20n is preferably a copper-depleted layer, a typical copper-rich target and a copper-deficient target are sequentially sputter-prepared. The preparation process of the CIGS light absorbing layer is: using Cu ₂ Se target as copper-rich target, (In, 0 ^ target as copper-deficient target; Cu ₂ Se target using RF sputtering, sputtering power density is 0.4 W cm" ² , The target distance is 8 cm, the working pressure is 0.8 Pa; (In, Ga) ₄ Se ₃ target is also RF sputtering, the sputtering power density is 2 W cm_ ² , the target distance is 8 cm, and the working pressure is 0.8 Pa; The prepared underlayer 201 layer is copper-depleted (In, Ga) ₄ Se ₃ , and then a copper-rich second 202-layer Cu ₂ Se is prepared, and a copper-depleted top layer 203 layer (In, Ga) ₄ Se _{3 is} again prepared. 1500 nm thick CIGS precursor film, Cu / (In + Ga) = 0.85, Ga / (In + Ga) = 0.30 in the film; in the 50 Pa of nitrogen, the precursor film is placed at the Se source temperature of 250 ° C In the saturated vapor pressure of Se, the temperature was rapidly raised to 550 ° C at 30 ° C / min and held for 20 min to prepare the desired CIGS light absorbing layer.

在所制备的 CIGS光吸收层表面通过化学浴沉积法制备 70 nm厚的 CdS层，再在其上通过溅射法制备 100 nm厚的 i-ZnO层和 600 nm厚的 ΖηΟ:Α1层，即得到 CIGS薄膜太阳电池。 A 70 nm thick CdS layer was prepared by chemical bath deposition on the surface of the prepared CIGS light absorbing layer, and then a 100 nm thick i-ZnO layer and a 600 nm thick ΖnΟ:Α1 layer were prepared by sputtering. Get a CIGS thin film solar cell.

下面介绍本发明的实施例，但本发明绝非限于实施例。 The embodiments of the present invention are described below, but the present invention is by no means limited to the embodiments.

实施例 1 : Example 1

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以 C_U。.₉In。.₈G_a。.₂S_ei.₉₅作为靶材，采用射频溅射法制备 CIGS前驱薄膜，溅射功率密度为 1.2 W cm_²，靶距为 7 cm, 工作气压为 1.2 Pa; 所制备的 CIGS前驱薄膜的厚度为 1200 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.86， Ga/(In+Ga)=0.20。 Preparation of a CIGS precursor film: on a molybdenum-coated soda-lime-silica glass, with C _U . . ₉ In. ₈ G _a . ₂ S _ei . ₉₅ as a target, the CIGS precursor film was prepared by RF sputtering, the sputtering power density was 1.2 W cm_ ² , the target distance was 7 cm, and the working pressure was 1.2 Pa. The thickness of the prepared CIGS precursor film For 1200 nm, Cu/(In+Ga)=0.86, Ga/(In+Ga)=0.20 in the prepared CIGS precursor film due to the difference in sputtering rate of the elements.

CIGS前驱薄膜热处理：在 30000 Pa的氮气中，将固态单质 Se源加热到 230°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 30°C/min的升温速度将 CIGS前驱薄膜加热到 530°C并保温 30 min, 即制备出所需的 CIGS光吸收层。所述 CIGS光吸收层可用于制备 CIGS薄膜太阳电池。在所制备的 CIGS光吸收层表面通过化学浴沉积法制备 70 nm厚的 CdS层，再在其上通过溅射法制备 100 nm厚的 i-ZnO层和 600 nm厚的 ΖηΟ:Α1层，即得到 CIGS薄膜太阳电池。 Heat treatment of CIGS precursor film: In a nitrogen gas of 30,000 Pa, the solid elemental Se source is heated to 230 ° C to form a saturated vapor pressure of Se, and the CIGS precursor film is placed in a saturated Se vapor pressure to raise the temperature at 30 ° C / min. The CIGS precursor film was heated to 530 ° C for 30 min to prepare the desired CIGS light absorbing layer. The CIGS light absorbing layer can be used to prepare a CIGS thin film solar cell. A 70 nm thick CdS layer was prepared by chemical bath deposition on the surface of the prepared CIGS light absorbing layer, and then a 100 nm thick i-ZnO layer and a 600 nm thick ΖηΟ:Α1 layer were prepared by sputtering. Get a CIGS thin film solar cell.

所制备的 CIGS薄膜太阳电池在 AMI .5标准太阳光下的光电转换效率为 7.3%。实施例 1的对比例： The photoelectric conversion efficiency of the prepared CIGS thin film solar cell under AMI .5 standard sunlight was 7.3%. Comparative Example of Example 1:

制备 CIGS前驱薄膜：将镀钼的钠钙硅玻璃加热至 200°C，其余制备条件同实施例 Preparation of CIGS precursor film: The molybdenum-plated soda-lime-silica glass was heated to 200 ° C, and the rest of the preparation conditions were the same as in the examples.

CIGS前驱薄膜热处理：不采用任何热处理。 CIGS precursor film heat treatment: no heat treatment is used.

CdS、 i-ZnO、 ΖηΟ:Α1层的制备同实施例 1。 The preparation of CdS, i-ZnO, ΖnΟ: Α1 layer was the same as in Example 1.

所制备的 CIGS薄膜太阳电池在 AMI .5标准太阳光下的光电转换效率为 1.2%。 The prepared CIGS thin film solar cell has a photoelectric conversion efficiency of 1.2% under AMI .5 standard sunlight.

实施例 2: Example 2:

制备 CIGS前驱薄膜：在镀钼的陶瓷板上，以 C_U。.₇In。.₆G_a。.₄S_ei.₈₅作为靶材，采用射频溅射法制备 CIGS前驱薄膜，溅射功率密度为 0.2 W cm_²，靶距为 4 cm, 工作气压为 0.05 Pa; 所制备的 CIGS前驱薄膜的厚度为 500 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.67， Ga/(In+Ga)=0.40。 Preparation of CIGS precursor film: On a molybdenum plated ceramic plate, with C _U . . ₇ In. . ₆ G _a . ₄ S _ei . ₈₅ as a target, the CIGS precursor film was prepared by RF sputtering, the sputtering power density was 0.2 W cm_ ² , the target distance was 4 cm, and the working pressure was 0.05 Pa. The thickness of the prepared CIGS precursor film For 500 nm, Cu/(In+Ga)=0.67, Ga/(In+Ga)=0.40 in the prepared CIGS precursor film due to the difference in sputtering rate of the elements.

CIGS前驱薄膜热处理：在 100000 Pa的氮气中，将固态单质 Se源加热到 180°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 10°C/min的升温速度将 CIGS前驱薄膜加热到 450°C并保温 60 min, 即制备出所需的 CIGS光吸收层。实施例 3 : Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C in 100000 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 10 ° C / min. The CIGS precursor film was heated to 450 ° C for 60 min to prepare the desired CIGS light absorbing layer. Example 3:

制备 CIGS前驱薄膜：在镀钼的不锈钢箔上，以 C_U。.₅In。.₃G_a。.₇S_ei.₇₅作为靶材，采用射频溅射法制备 CIGS前驱薄膜，溅射功率密度为 3.0 W cm_²，靶距为 10 cm, 工作气压为 5 Pa; 所制备的 CIGS前驱薄膜的厚度为 1500 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.49， Ga/(In+Ga)=0.70。 Preparation of CIGS precursor film: On a molybdenum-plated stainless steel foil, with C _U . . ₅ In. . ₃ G _a . ₇ S _ei . ₇₅ as a target, the CIGS precursor film was prepared by RF sputtering, the sputtering power density was 3.0 W cm_ ² , the target distance was 10 cm, and the working pressure was 5 Pa. The thickness of the prepared CIGS precursor film At 1500 nm, Cu/(In+Ga)=0.49, Ga/(In+Ga)=0.70 in the prepared CIGS precursor film due to the difference in sputtering rate of the elements.

CIGS前驱薄膜热处理：在 10000 Pa的氮气中，将固态单质 Se源加热到 350°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 50°C/min的升温速度将 CIGS前驱薄膜加热到 500°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 4: Heat treatment of CIGS precursor film: In a nitrogen gas of 10000 Pa, the solid elemental Se source is heated to 350 ° C to form a saturated vapor pressure of Se, and the CIGS precursor film is placed in a saturated Se vapor pressure to raise the temperature at 50 ° C / min. Speed The CIGS precursor film was heated to 500 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 4:

制备 CIGS前驱薄膜：在镀钼的钛箔上，以 C_UIn。.。₅G_a。.₉₅S_ei.₅。作为靶材，采用射频溅射法制备 CIGS前驱薄膜，溅射功率密度为 10.0 W cm"², 靶距为 20 cm, 工作气压为 20 Pa; 所制备的 CIGS前驱薄膜的厚度为 2500 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.96， Ga/(In+Ga)=0.95。 Preparation of CIGS precursor film: On a molybdenum-plated titanium foil, C _U In. . . . ₅ G _a . ₉₅ S _ei . ₅ . As a target, a CIGS precursor film was prepared by RF sputtering. The sputtering power density was 10.0 W cm" ² , the target distance was 20 cm, and the working pressure was 20 Pa. The thickness of the prepared CIGS precursor film was 2500 nm. The difference in the sputtering rate of the elements was Cu/(In+Ga)=0.96, Ga/(In+Ga)=0.95 in the prepared CIGS precursor film.

CIGS前驱薄膜热处理：在 5 Pa的氮气中，将固态单质 Se源加热到 450°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 lOOtVmin的升温速度将 CIGS前驱薄膜加热到 600°C并保温 10 min, 即制备出所需的 CIGS光吸收层。实施例 5: Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 450 ° C in 5 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure, and the CIGS precursor is heated at a heating rate of 100 tVmin. The film was heated to 600 ° C and held for 10 min to prepare the desired CIGS light absorbing layer. Example 5

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以 Cu₂Se和 Cu(In, Ga)₅Se₈作为靶材，分别采用直流和射频同时溅射制备 CIGS前驱薄膜，溅射功率密度均为 3.5 W cm"², 靶距均为 8 cm, 工作气压为 5.5 Pa; 所制备的 CIGS前驱薄膜的厚度为 1600 nm。 Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, Cu ₂ Se and Cu(In, Ga) ₅ Se ₈ were used as targets, and the CIGS precursor film was prepared by simultaneous DC and RF sputtering, respectively. Both are 3.5 W cm" ² , the target distance is 8 cm, and the working pressure is 5.5 Pa. The thickness of the prepared CIGS precursor film is 1600 nm.

CIGS前驱薄膜热处理：在 30000 Pa的氮气中，将固态单质 Se源加热到 230°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 30°C/min的升温速度将 CIGS前驱薄膜加热到 500°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 6 : Heat treatment of CIGS precursor film: In a nitrogen gas of 30,000 Pa, the solid elemental Se source is heated to 230 ° C to form a saturated vapor pressure of Se, and the CIGS precursor film is placed in a saturated Se vapor pressure to raise the temperature at 30 ° C / min. Speed The CIGS precursor film was heated to 500 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 6:

制备 CIGS前驱薄膜：在镀钼的聚酰亚胺膜上，以 Cu和 (In, Ga)₄Se₃作为靶材，分别采用直流和射频同时溅射制备 CIGS前驱薄膜，溅射功率密度均为 0.2 W cm"², 靶距均为 4 cm，工作气压为 0.05 Pa; 所制备的 CIGS前驱薄膜的厚度为 600 nm。 Preparation of CIGS precursor film: On the molybdenum-coated polyimide film, Cu and (In, Ga) ₄ Se ₃ were used as targets, and the CIGS precursor film was prepared by simultaneous DC and RF sputtering, respectively. 0.2 W cm" ² , the target distance is 4 cm, the working pressure is 0.05 Pa; the thickness of the prepared CIGS precursor film is 600 nm.

CIGS前驱薄膜热处理：在 100000 Pa的氮气中，将固态单质 Se源加热到 180°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 10°C/min的升温速度将 CIGS前驱薄膜加热到 450°C并保温 60 min, 即制备出所需的 CIGS光吸收层。实施例 7: Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C in 100000 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 10 ° C / min. The CIGS precursor film was heated to 450 ° C for 60 min to prepare the desired CIGS light absorbing layer. Example 7

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以 Cu^In, Ga)Se₂ P Cu₂(In, Ga)₄Se₇作为靶材，分别采用直流和射频同时溅射制备 CIGS前驱薄膜，溅射功率密度均为 5.0 W cm_²，靶距均为 12 cm, 工作气压为 10 Pa; 所制备的 CIGS前驱薄膜的厚度为 2000 mn。 Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, Cu^In, Ga)Se ₂ P Cu ₂ (In, Ga) ₄ Se _{7 was} used as the target, and the CIGS precursor was prepared by simultaneous DC and RF sputtering. The film, sputtering power density is 5.0 W cm_ ² , the target distance is 12 cm, the working pressure is 10 Pa; the thickness of the prepared CIGS precursor film is 2000 mn.

CIGS前驱薄膜热处理：在 100 Pa的氮气中，将固态单质 Se源加热到 350°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 50°C/min的升温速度将 CIGS前驱薄膜加热到 500°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 8 : Heat treatment of CIGS precursor film: heating the solid elemental Se source to 350 ° C in 100 Pa of nitrogen, The saturated vapor pressure of Se is placed, the CIGS precursor film is placed in a saturated Se vapor pressure, and the CIGS precursor film is heated to 500 ° C at a heating rate of 50 ° C / min and held for 30 min to prepare the desired CIGS light. Absorbing layer. Example 8:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以 Cu₂(In, Ga)Se₃和 Cu。.₅(In, Ga)S_ei.₇₅作为靶材，分别采用直流和射频同时溅射制备 CIGS前驱薄膜，溅射功率密度均为 10.0 W cm"², 靶距均为 20 cm, 工作气压为 20 Pa; 所制备的 CIGS前驱薄膜的厚度为 2400 mn。 Preparation of CIGS precursor film: On molybdenum-coated soda-lime-silica glass, Cu ₂ (In, Ga) Se ₃ and Cu were used. ₅ (In, Ga)S _ei . ₇₅ as a target, respectively, using DC and RF simultaneous sputtering to prepare CIGS precursor film, the sputtering power density is 10.0 W cm" ² , the target distance is 20 cm, the working pressure is 20 Pa; The prepared CIGS precursor film has a thickness of 2400 mn.

CIGS前驱薄膜热处理：在 5 Pa的氮气中，将固态单质 Se源加热到 450°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 lOOtVmin的升温速度将 CIGS前驱薄膜加热到 600°C并保温 10 min, 即制备出所需的 CIGS光吸收层。实施例 9 : Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 450 ° C in 5 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure, and the CIGS precursor is heated at a heating rate of 100 tVmin. The film was heated to 600 ° C and held for 10 min to prepare the desired CIGS light absorbing layer. Example 9:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 C_U(I_n。.₇G_a。.₃)₃S_e5为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 1.2 W cm_²，靶距为 7 cm,工作气压为 1.2 Pa; 以富铜靶 Cu₂Se作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 1.2 W cm_²，靶距为 7 cm，工作气压为 1.2 Pa; 以 Preparation of CIGS precursor film: on the molybdenum-coated soda-lime-silica glass, using the copper-deficient target C _U (I _n .. ₇ G _a .. ₃ ) ₃ S _e5 as the target, the copper-depleted phase CIGS was prepared by RF sputtering. The precursor film 201 has a sputtering power density of 1.2 W cm_ ² , a target distance of 7 cm, and a working pressure of 1.2 Pa. Using a copper-rich target Cu ₂ Se as a target, a copper-rich phase CIGS precursor film 202 is prepared by direct current sputtering. , sputtering power density is 1.2 W cm_ ² , target distance is 7 cm, working pressure is 1.2 Pa;

C_U(I_n。.₇G_a。.₃)₃S_e5作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 1.2 W cm_²，靶距为 7 cm，工作气压为 1.2 Pa; 所制备的 CIGS前驱薄膜的厚度为 1200 nm，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.86， Ga/(In+Ga)=0.30。 C _U (I _n .. ₇ G _a .. ₃ ) ₃ S _e5 as a target, a copper-depleted phase CIGS precursor film 203 was prepared by RF sputtering, with a sputtering power density of 1.2 W cm_ ² and a target distance of 7 cm. The working pressure is 1.2 Pa; the thickness of the prepared CIGS precursor film is 1200 nm, and the prepared CIGS precursor film has Cu/(In+Ga)=0.86, Ga/(In+Ga)=0.30.

CIGS前驱薄膜热处理：在 30000 Pa的氮气中，将固态单质 Se源加热到 250°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 30°C/min的升温速度将 CIGS前驱薄膜加热到 550°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 10 : Heat treatment of CIGS precursor film: In a nitrogen gas of 30,000 Pa, the solid elemental Se source is heated to 250 ° C to form a saturated vapor pressure of Se, and the CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 30 ° C / min. Speed The CIGS precursor film was heated to 550 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 10:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 (In, Ga)₄Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 0.2 W cm_²，靶距为 4 cm, 工作气压为 0.05 Pa; 以富铜靶 CuSe作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 0.2 W cm"², 靶距为 4 cm, 工作气压为 0.05 Pa; 以 (In, Ga)₄Se₃作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 0.2 W cm"², 靶距为 4 cm, 工作气压为 0.05 Pa; 所制备的 CIGS前驱薄膜的厚度为 500 nm。 Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, a copper-depleted phase CIGS precursor film 201 was prepared by radio frequency sputtering using a copper-deficient target (In, Ga) ₄ Se ₃ as a target. The sputtering power density was 0.2 W cm_ ² , target distance is 4 cm, working pressure is 0.05 Pa; copper-rich target CIGS precursor film 202 is prepared by DC sputtering with Cu-rich target CuSe as target. The sputtering power density is 0.2 W cm" ² , the target distance is 4 cm, the working pressure is 0.05 Pa; using (In, Ga) ₄ Se ₃ as the target, the copper-depleted phase CIGS precursor film 203 is prepared by RF sputtering, and the sputtering power density is 0.2 W cm" ² , the target distance is 4 cm, the working pressure is 0.05 Pa; the thickness of the prepared CIGS precursor film is 500 Nm.

CIGS前驱薄膜热处理：在 100000 Pa的氮气中，将固态单质 Se源加热到 180°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 10°C/min的升温速度将 CIGS前驱薄膜加热到 450°C并保温 60 min, 即制备出所需的 CIGS光吸收层。实施例 11 : Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C in 100000 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 10 ° C / min. The CIGS precursor film was heated to 450 ° C for 60 min to prepare the desired CIGS light absorbing layer. Example 11:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 (In, Ga)₂Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 5 W cm_²，靶距为 15 cm，工作气压为 5 Pa; 以富铜靶 Cu (In, Ga)Se作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 5 W cm_²，靶距为 15 cm，工作气压为 5 Pa;以 (In, Ga)₂Se₃ 作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 5 W cm"², 靶距为 15 cm, 工作气压为 5 Pa; 所制备的 CIGS前驱薄膜的厚度为 1500 nm。 Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, the copper-depleted phase CIGS precursor film 201 was prepared by radio frequency sputtering using the copper-deficient target (In, Ga) ₂ Se ₃ as the target. The sputtering power density was 5 W cm_ ² , target distance 15 cm, working pressure 5 Pa; copper-rich target Cu (In, Ga) Se as target, copper-rich phase CIGS precursor film 202 by DC sputtering, sputtering power density It is 5 W cm_ ² , the target distance is 15 cm, and the working pressure is 5 Pa. Using (In, Ga) ₂ Se ₃ as the target, the copper-depleted phase CIGS precursor film 203 is prepared by RF sputtering. The sputtering power density is 5 W cm" ² with a target distance of 15 cm and a working pressure of 5 Pa; the prepared CIGS precursor film has a thickness of 1500 nm.

CIGS前驱薄膜热处理：在 100 Pa的氮气中，将固态单质 Se源加热到 350°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 50°C/min的升温速度将 CIGS前驱薄膜加热到 500°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 12: Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 350 ° C in 100 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure to raise the temperature at 50 ° C / min. Speed The CIGS precursor film was heated to 500 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 12:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 C_Ul.₅(In, Ga)S_ei.₇₅为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 10 W cm_²，靶距为 20 cm,工作气压为 20 Pa;以富铜靶 Cu₂Se作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 10 W cm"²,靶距为 20 cm,工作气压为 20 Pa;以 Cu^CIn, Ga)S_ei.₇₅作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 10 W cm_²，靶距为 20 cm，工作气压为 20 Pa; 所制备的 CIGS前驱薄膜的厚度为 2500 nm。 Preparation of CIGS precursor film: on the molybdenum-coated soda-lime-silica glass, using the copper-deficient target C _Ul . ₅ (In, Ga)S _ei . ₇₅ as the target, the copper-depleted phase CIGS precursor film 201 was prepared by RF sputtering. The sputtering power density is 10 W cm_ ² , the target distance is 20 cm, and the working pressure is 20 Pa. Using the copper-rich target Cu ₂ Se as the target, the copper-rich phase CIGS precursor film 202 is prepared by DC sputtering. The density is 10 W cm" ² , the target distance is 20 cm, the working pressure is 20 Pa; using Cu^CIn, Ga)S _ei . ₇₅ as the target, the copper-depleted phase CIGS precursor film 203 is prepared by RF sputtering. The power density is 10 W cm_ ² , the target distance is 20 cm, and the working pressure is 20 Pa. The thickness of the prepared CIGS precursor film is 2500 nm.

CIGS前驱薄膜热处理：在 5 Pa的氮气中，将固态单质 Se源加热到 450°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 lOOtVmin的升温速度将 CIGS前驱薄膜加热到 600°C并保温 10 min, 即制备出所需的 CIGS光吸收层。实施例 13: Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 450 ° C in 5 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure, and the CIGS precursor is heated at a heating rate of 100 tVmin. The film was heated to 600 ° C and held for 10 min to prepare the desired CIGS light absorbing layer. Example 13

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 (In, Ga)₄Se₃和 Preparation of CIGS precursor film: on molybdenum-coated soda-lime-silica glass, with copper-poor target (In, Ga) ₄ Se ₃ and

C_U(I_n。.₇G_a。.₃)₃S_e5为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 1.2 W cm"², 靶距为 7 cm, 工作气压为 1.2 Pa; 以富铜靶 Cu₂Se和 Cu(In, Ga)Se₂ 作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 202，溅射功率密度为 1.2 W cm— ²，靶距为 7 cm，工作气压为 1.2 Pa; 以 (In, Ga)₄Se₃和 Cu(In。.₇Ga。.₃;>₃Se₅作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 1.2 W cm_²，靶距为 7 cm, 工作气压为 1.2 Pa; 所制备的 CIGS前驱薄膜的厚度为 1200 nm，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.86， Ga/(In+Ga)=0.30。 C _U (I _n .. ₇ G _a .. ₃ ) ₃ S _e5 is the target, the copper-depleted phase CIGS precursor film 201 is prepared by RF sputtering, sputtering power The density is 1.2 W cm" ² , the target distance is 7 cm, and the working pressure is 1.2 Pa. Using copper-rich target Cu ₂ Se and Cu(In, Ga) Se ₂ as targets, the copper-rich phase CIGS is prepared by DC sputtering. The precursor film 202 has a sputtering power density of 1.2 W cm - ² , a target distance of 7 cm, and a working gas pressure of 1.2 Pa; (In, Ga) ₄ Se ₃ and Cu (In. ₇ Ga.. ₃ ; > ₃ Se _{5 was} used as a target to prepare a copper-depleted phase CIGS precursor film 203 by RF sputtering. The sputtering power density was 1.2 W cm_ ² , the target distance was 7 cm, and the working pressure was 1.2 Pa. The thickness of the prepared CIGS precursor film At 1200 nm, Cu/(In+Ga)=0.86, Ga/(In+Ga)=0.30 in the prepared CIGS precursor film.

CIGS前驱薄膜热处理：在 30000 Pa的氮气中，将固态单质 Se源加热到 250°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 30°C/min的升温速度将 CIGS前驱薄膜加热到 550°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 14 : Heat treatment of CIGS precursor film: In a nitrogen gas of 30,000 Pa, the solid elemental Se source is heated to 250 ° C to form a saturated vapor pressure of Se, and the CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 30 ° C / min. Speed The CIGS precursor film was heated to 550 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 14:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 C_U(I_n。.₇G_a。.₃)₅S_e8为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 1.2 W cm_²，靶距为 7 cm, 工作气压为 1.2 Pa; 以富铜靶 C_U。.₉(I_n。.₇Ga。.₃;)₇S_e3作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 202，溅射功率密度为 1.2 W cm_²，靶距为 7 cm, 工作气压为 1.2 Pa; 以贫铜靶 C_U(I_nQ.₇G_aQ.₃)₅Se₈作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 1.2 W cm_²，靶距为 7 cm，工作气压为 1.2 Pa; 以富铜靶 C_U().₉(I_n。.₇G_a。.₃)₇S_e3作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 204，溅射功率密度为 1.2 W cm"², 靶距为 7 cm, 工作气压为 1.2 Pa; 以贫铜靶 Cu(In。.₇Ga。.₃;)₅Se₈作为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 205，溅射功率密度为 1.2 W cm— ²，靶距为 7 cm，工作气压为 1.2 Pa; 所制备的 CIGS前驱薄膜的厚度为 1200 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga;>=0.86， Ga/(In+Ga)=0.30 _o CIGS precursor film was prepared: on a Mo-coated soda-lime-silica glass, a copper target lean _{_{_{C U (I n .. 7 G}}} a .. 3) 5 S e8 as a target, a copper-depleted phase were prepared RFSputtering CIGS The precursor film 201 has a sputtering power density of 1.2 W cm_ ² , a target distance of 7 cm, a working pressure of 1.2 Pa, and a copper-rich target C _U . ₉ (I _n .. ₇ Ga.. ₃ ;) ₇ S _e3 as a target, a copper-rich phase CIGS precursor film 202 was prepared by DC sputtering, with a sputtering power density of 1.2 W cm_ ² and a target distance of 7 cm. The working pressure is 1.2 Pa; the copper-depleted phase CI GS precursor film 203 is prepared by radio frequency sputtering using a copper-deficient target C _U (I _nQ . ₇ G _aQ . ₃ ) ₅ Se ₈ as a target, and the sputtering power density is 1.2. W cm_ ² , target distance of 7 cm, working pressure is 1.2 Pa; using copper-rich target C _U() . ₉ (I _n .. ₇ G _a .. ₃ ) ₇ S _e3 as target, using DC sputtering A copper-rich phase CIGS precursor film 204 was prepared, having a sputtering power density of 1.2 W cm" ² , a target distance of 7 cm, a working gas pressure of 1.2 Pa, and a copper-depleted target Cu (In. ₇ Ga.. ₃ ;) ₅ Se ₈ as a target, the copper-depleted phase CIGS precursor film 205 was prepared by RF sputtering. The sputtering power density was 1.2 W cm - ² , the target distance was 7 cm, and the working pressure was 1.2 Pa. The thickness of the prepared CIGS precursor film was as follows. 1200 nm, due to the difference in sputtering rate of elements, Cu/(In+Ga;>=0.86, Ga/(In+Ga)=0.30 _{o in} the prepared CIGS precursor film

CIGS前驱薄膜热处理：在 30000 Pa的氮气中，将固态单质 Se源加热到 250°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 30°C/min的升温速度将 CIGS前驱薄膜加热到 550°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 15 : Heat treatment of CIGS precursor film: In a nitrogen gas of 30,000 Pa, the solid elemental Se source is heated to 250 ° C to form a saturated vapor pressure of Se, and the CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 30 ° C / min. Speed The CIGS precursor film was heated to 550 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 15:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 (In, Ga)₄Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 0.2 W cm_²，靶距为 4 cm, 工作气压为 0.05 Pa; 以富铜靶 CuSe作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 0.2 W cm_²，靶距为 4 cm，工作气压为 0.05 Pa; 以贫铜靶 (In, Ga)₄Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 0.2 W cm_²，靶距为 4 cm，工作气压为 0.05 Pa; 以富铜靶 CuSe作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 204，溅射功率密度为 0.2 W cm"²,靶距为 4 cm, 工作气压为 0.05 Pa; 以贫铜靶 (In, Ga)₄Se₃为靶材，采用射频溅射法制备贫铜相 CIGS 前驱薄膜 205，溅射功率密度为 0.2 W cm_²，靶距为 4 cm, 工作气压为 0.05 Pa; 所制备的 CIGS前驱薄膜的厚度为 1200 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.86， Ga/(In+Ga)=0.30。 Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, a copper-depleted phase CIGS precursor film 201 was prepared by radio frequency sputtering using a copper-deficient target (In, Ga) ₄ Se ₃ as a target. The sputtering power density was 0.2 W cm_ ² , target distance is 4 cm, working pressure is 0.05 Pa; copper-rich target CuGS is used as target, copper-rich phase CIGS precursor film 202 is prepared by DC sputtering, and the sputtering power density is 0.2 W cm_ ² . Target distance is 4 cm, working pressure is 0.05 Pa; The copper target (In, Ga) ₄ Se ₃ is used as a target, and the copper-depleted phase CIGS precursor film 203 is prepared by RF sputtering. The sputtering power density is 0.2 W cm_ ² , the target distance is 4 cm, and the working pressure is 0.05 Pa. Copper-rich phase CIGS precursor film 204 was prepared by DC sputtering using a copper-rich target CuSe as a target. The sputtering power density was 0.2 W cm" ² , the target distance was 4 cm, and the working pressure was 0.05 Pa. (In, Ga) ₄ Se ₃ is used as a target, and the copper-depleted phase CIGS precursor film 205 is prepared by RF sputtering. The sputtering power density is 0.2 W cm_ ² , the target distance is 4 cm, and the working pressure is 0.05 Pa. The thickness of the CIGS precursor film is 1200 nm. Due to the difference in sputtering rate of the elements, the prepared CIGS precursor film has Cu/(In+Ga)=0.86, Ga/(In+Ga)=0.30.

CIGS前驱薄膜热处理：在 100000 Pa的氮气中，将固态单质 Se源加热到 180°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 10°C/min的升温速度将 CIGS前驱薄膜加热到 450°C并保温 60 min, 即制备出所需的 CIGS光吸收层。实施例 16 : Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C in 100000 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure at a temperature of 10 ° C / min. The CIGS precursor film was heated to 450 ° C for 60 min to prepare the desired CIGS light absorbing layer. Example 16:

制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 (In, Ga)₂Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 5 W cm_²，靶距为 15 cm，工作气压为 5 Pa; 以富铜靶 Cu (In, Ga)Se作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 5 W cm_²，靶距为 15 cm，工作气压为 5 Pa; 以贫铜靶 (In, Ga)₂Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 5 W cm"², 靶距为 15 cm, 工作气压为 5 Pa; 以富铜靶 Cu (In, Ga)Se作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 204，溅射功率密度为 5 W cm"², 靶距为 15 cm, 工作气压为 5 Pa; 以贫铜靶 (In, Ga)₂Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 205，溅射功率密度为 5 W cm_²，靶距为 15 cm，工作气压为 5 Pa; 以富铜靶 Cu (In, Ga)Se作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 206，溅射功率密度为 5 W cm_²，靶距为 15 cm, 工作气压为 5 Pa; 以贫铜靶 (In, Ga)₂Se₃为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 207，溅射功率密度为 5 W cm"², 靶距为 15 cm, 工作气压为 5 Pa;所制备的 CIGS前驱薄膜的厚度为 1800 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.86， Ga/(In+Ga)=0.30。 Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, the copper-depleted phase CIGS precursor film 201 was prepared by radio frequency sputtering using the copper-deficient target (In, Ga) ₂ Se ₃ as the target. The sputtering power density was 5 W cm_ ² , target distance 15 cm, working pressure 5 Pa; copper-rich target Cu (In, Ga) Se as target, copper-rich phase CIGS precursor film 202 by DC sputtering, sputtering power density 5 W cm_ ² , target distance 15 cm, working pressure 5 Pa; using copper-deficient target (In, Ga) ₂ Se ₃ as target, preparation of copper-depleted phase CIGS precursor film 203 by RF sputtering, sputtering The power density is 5 W cm" ² , the target distance is 15 cm, and the working pressure is 5 Pa. Using the copper-rich target Cu (In, Ga) Se as the target, the copper-rich phase CIGS precursor film 204 is prepared by DC sputtering. The sputtering power density is 5 W cm" ² , the target distance is 15 cm, and the working pressure is 5 Pa. Using the copper-deficient target (In, Ga) ₂ Se ₃ as the target, the copper-depleted phase CIGS precursor is prepared by RF sputtering. film 205, the sputtering power density of 5 W cm_ ^2, a target distance of 15 cm, operating pressure of 5 Pa; target copper-rich Cu (in, Ga) Se as a target, DC sputtering with Cu-rich CIGS Preparation Driving film 206, the sputtering power density of 5 W cm_ ^2, a target distance of 15 cm, operating pressure of 5 Pa; lean copper target (In, Ga) ₂ Se ₃ as a target, by RF Sputtering copper poor Phase CIGS precursor film 207, sputtering power density is 5 W cm" ² , target distance is 15 cm, working pressure is 5 Pa; the thickness of the prepared CIGS precursor film is 1800 nm, due to the difference in sputtering rate of elements The prepared CIGS precursor film had Cu/(In+Ga)=0.86, Ga/(In+Ga)=0.30.

CIGS前驱薄膜热处理：在 100 Pa的氮气中，将固态单质 Se源加热到 350°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 30°C /min的升温速度将 CIGS前驱薄膜加热到 500°C并保温 30 min, 即制备出所需的 CIGS光吸收层。实施例 17 : 制备 CIGS前驱薄膜：在镀钼的钠钙硅玻璃上，以贫铜靶 (Ii^Gao ^Ses为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 201，溅射功率密度为 2 W cm"²,靶距为 7.5 cm, 工作气压为 0.5 Pa; 以富铜靶 CuSe作为靶材，采用直流溅射法制备富铜相 CIGS 前驱薄膜 202，溅射功率密度为 2 W cm_²，靶距为 7.5 cm，工作气压为 0.5 Pa; 以贫铜靶 (In^Gao.^Ses为靶材，采用射频溅射法制备贫铜相 CIGS前驱薄膜 203，溅射功率密度为 2 W cm_²，靶距为 7.5 cm，工作气压为 0.5 Pa; 以富铜靶 CuSe作为靶材，采用直流溅射法制备富铜相 CIGS前驱薄膜 204，溅射功率密度为 2 W cm_²，靶距为 7.5 cm, 工作气压为 0.5 Pa; 以贫铜靶 (I_n。.₅G_a。.₅)₄Se₃为靶材，采用射频溅射法制备贫铜相 CIGS 前驱薄膜 205，溅射功率密度为 2 W cm_²，靶距为 7.5 cm，工作气压为 0.5 Pa; 所制备的 CIGS前驱薄膜的厚度为 1500 nm，由于元素溅射率的差异，所制备的 CIGS前驱薄膜中 Cu/(In+Ga)=0.89， Ga/(In+Ga)=0.29。 Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 350 ° C in 100 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure to raise the temperature at 30 ° C /min. Speed The CIGS precursor film was heated to 500 ° C and held for 30 min to prepare the desired CIGS light absorbing layer. Example 17: Preparation of CIGS precursor film: On the molybdenum-coated soda-lime-silica glass, a copper-depleted target (Ii^Gao^Ses as a target, a copper-depleted phase CIGS precursor film 201 was prepared by RF sputtering, and the sputtering power density was 2 W. Cm" ² , target distance is 7.5 cm, working pressure is 0.5 Pa; copper-rich target CuSe is used as target, copper-rich phase CIGS precursor film 202 is prepared by DC sputtering, sputtering power density is 2 W cm_ ² , target The working distance is 7.5 cm and the working pressure is 0.5 Pa. The copper-deficient target (In^Gao.^Ses is used as the target, and the copper-depleted phase CIGS precursor film 203 is prepared by RF sputtering. The sputtering power density is 2 W cm_ ² . The target distance is 7.5 cm and the working pressure is 0.5 Pa. The copper-rich target CIGS precursor film 204 is prepared by DC sputtering with Cu-rich target CuSe as the target. The sputtering power density is 2 W cm_ ² and the target distance is 7.5 cm. Working pressure is 0.5 Pa; using copper-deficient target (I _n .. ₅ G _a .. ₅ ) ₄ Se ₃ as target, the copper-depleted phase CIGS precursor film 205 is prepared by RF sputtering, and the sputtering power density is 2 W cm_ ² , target distance is 7.5 cm, working pressure is 0.5 Pa; the thickness of the prepared CIGS precursor film is 1500 nm, due to elemental sputtering rate The difference was that Cu/(In+Ga)=0.89, Ga/(In+Ga)=0.29 in the prepared CIGS precursor film.

CIGS前驱薄膜热处理：在 15000 Pa的氮气中，将固态单质 Se源加热到 320°C，形成 Se的饱和蒸汽压，将 CIGS前驱薄膜置于饱和 Se蒸汽压中，以 80°C/min的升温速度将 CIGS前驱薄膜加热到 560°C并保温 25 min, 即制备出所需的 CIGS光吸收层。 Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 320 ° C in 15000 Pa of nitrogen to form a saturated vapor pressure of Se. The CIGS precursor film is placed in a saturated Se vapor pressure to raise the temperature at 80 ° C / min. Speed The CIGS precursor film was heated to 560 ° C and held for 25 min to prepare the desired CIGS light absorbing layer.

CdS、 i-ZnO和 ΖηΟ:Α1层的制备同实施例 1。 The preparation of CdS, i-ZnO and ΖηΟ: Α1 layers was the same as in Example 1.

所制备的 CIGS薄膜太阳电池，在 AMI .5标准太阳光下，测得的光电转换效率为 12.8%, 电池的 J-V曲线如图 4所示。实施例 17的对比例 1 : The prepared CIGS thin film solar cell has a photoelectric conversion efficiency of 12.8% measured under AMI .5 standard sunlight, and the J-V curve of the battery is shown in Fig. 4. Comparative Example 1 of Example 17:

制备 CIGS前驱薄膜：将镀钼的钠钙硅玻璃加热到 200°C，其余制备条件同实施例 Preparation of CIGS precursor film: The molybdenum-plated soda-lime-silica glass was heated to 200 ° C, and the rest of the preparation conditions were the same as in the examples.

17。 17.

CIGS前驱薄膜热处理同实施例 17。 The heat treatment of the CIGS precursor film was the same as in Example 17.

所制备的 CIGS薄膜太阳电池在 AMI .5标准太阳光下的光电转换效率为 6.4%。实施例 17的对比例 2: The prepared CIGS thin film solar cell has a photoelectric conversion efficiency of 6.4% under AMI .5 standard sunlight. Comparative Example 2 of Example 17:

制备 CIGS前驱薄膜：贫铜靶全部采用 (I_n。.₇G_a。.₃)₄S_e3，其余制备条件同实施例 17，此时所制备的 CIGS前驱膜 Ga没有梯度分布。 Preparation of CIGS precursor film: The copper-deficient target was all used (I _n .. ₇ G _a . . . ₃ ) ₄ S _e3 , and the other preparation conditions were the same as those in Example 17, and the prepared CIGS precursor film Ga had no gradient distribution.

CdS、 i-ZnO和 ΖηΟ:Α1层的制备同实施例 1。所制备的 CIGS薄膜太阳电池在 AMI .5标准太阳光下的光电转换效率为 10.2%_t 实施例 17的对比例 3: The preparation of CdS, i-ZnO and ΖnΟ: Α1 layers was the same as in Example 1. CIGS thin film solar cells produced in the photoelectric conversion efficiency of sunlight standard AMI .5 to 10.2% _t embodiment of the Comparative Example 3 Example 17:

制备 CIGS前驱薄膜：贫铜靶全部采用 In₄Se₃，其余制备条件同实施例 17，此时所制备的 CIGS前驱膜没有 Ga。 Preparation of CIGS precursor film: The copper-deficient target was all In ₄ Se ₃ , and the other preparation conditions were the same as those in Example 17. The CIGS precursor film prepared at this time had no Ga.

所制备的 CIGS薄膜太阳电池在 AMI .5标准太阳光下的光电转换效率为 8.4%。 The prepared CIGS thin film solar cell has a photoelectric conversion efficiency of 8.4% under AMI .5 standard sunlight.

Claims

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A method for preparing a light absorption layer of a CIGS thin film solar cell, characterized in that: a CIGS precursor film is prepared by magnetron sputtering, and then heat-treated to prepare a CIGS film. Specifically, the following process steps are included:

(1) preparing a CIGS precursor film: a CIGS precursor film (200) is prepared by magnetron sputtering on a bottom electrode by single target sputtering, a copper-rich target, and a copper-deficient target simultaneously or sequentially;

(2) Heat treatment of CIGS precursor film: The solid elemental Se source is heated to 180 ° C ~ 450 ° C in a vacuum or a certain pressure of inert atmosphere to form a saturated vapor pressure of Se, and the CIGS precursor film prepared in step 1 is placed. In a saturated Se vapor pressure, the temperature is rapidly increased from 450 ° C to 600 ° C at a heating rate of 10 ° C / min to 100 ° C / min and held for 10 min to 60 min to prepare a light absorbing layer of a CIGS thin film solar cell;

Wherein, the target of 1 single target sputtering is Cu CIn, Ga) Se ₂ . _x/2 , where 0.05 x 0.50;

2 the copper-rich target is Cu, CuSe, Cu ₂ Se and Cu _1+x (In, Ga)Se _2+x/2 , wherein one or a mixture of 0.1 x 1.0 is mixed;

The copper-deficient target is (In, Ga) ₄ Se ₃ , (In, Ga) ₂ Se ₃ , Cu(In, Ga) ₅ Se ₈ , Cu(In, Ga) ₃ Se ₅ , Cu ₂ (In,

Ga) ₄ Se ₇ , Cu ₃ (In, Ga) ₅ Se ₉ and Cu _1-x (In, Ga)Se _2-x/2 , a mixture of one or more of 0.4 x 1.0.

2. The preparation method according to claim 1, characterized in that in the step 1, the method is prepared as follows

CIGS precursor film (200

Preparing a CIGS precursor film by single-target sputtering on a bottom electrode by magnetron sputtering; or

A CIGS precursor film is prepared by magnetron sputtering on the bottom electrode by magnetron sputtering using a copper-rich target and a copper-deficient target; or

A CIGS precursor film was prepared by magnetron sputtering on the bottom electrode by a sputtering process using a copper-rich target and a copper-poor target.

3. The preparation method according to claim 1, wherein when the copper-rich target and the copper-deficient target are sequentially sputtered in step 1, a laminated structure in which a copper-rich layer and a copper-depleted layer alternately are formed, and the bottom layer is Copper-rich or copper-depleted, top layer is copper-rich or copper-depleted.

4. The method according to claim 3, wherein the top layer is a copper-depleted layer.

5. The preparation method according to claim 3, wherein the total number of layers of the copper-rich layer and the copper-depleted layer is 2 to 12 layers, and the thickness of the single layer of the copper-rich layer and the copper-depleted layer is 10 nm to 1500 nm. .

6. The method according to claim 5, wherein the total number of layers of the copper-rich layer and the copper-depleted layer is 3-6, and the thickness of the single layer of the copper-rich layer and the copper-depleted layer is 50-1000 nm.

7. The preparation method according to claim 1 or 2, characterized in that:

a) In the preparation step (1), the single target sputtering is performed by radio frequency sputtering. The parameters of the RF sputtering are a power density of 0.2 W cm ^{-2 to} 10 W cm" ² , a target distance of 4 cm to 20 cm, and a working pressure of 0.05Pa~20Pa;

b) In the preparation step (1), the copper-rich target is subjected to direct current sputtering or radio frequency sputtering, and the sputtering process parameters are sputtering power density of 0.2 W cm ^{-2 to} 10 W cm" ² , and the target distance is 4 cm to 20 cm. , the working pressure is 0.05Pa~20Pa;

c) In the preparation step (1), the copper-deficient target is subjected to RF sputtering, and the sputtering process parameters are sputtering power density of 0.2 W cm ^{-2 to} 10 W cm" ² , target distance is 4 cm to 20 cm, and working pressure is 0.05Pa~20Pa.

8. The method according to claim 1, wherein:

a) In the preparation step (1), the single target sputtering is performed by radio frequency sputtering, and the single target sputtering process parameter is a sputtering power density of 0.5 W cm ^{-2 to} 5 W cm" ² , and the target distance is 5 cm to 15 cm. , the working pressure is 0.2Pa~10Pa;

b) In the preparation step (1), the sputtering process parameters of the copper-rich target using direct current sputtering or radio frequency sputtering are sputtering power density of 0.5 W cm_ ² 〜 5 W cm" ² , and the target distance is 5 cm 15 Cm, working pressure is 0.2Pa~10Pa;

c) In the preparation step (1), the sputtering process parameters of the copper-depleted target using RF sputtering are a sputtering power density of 0.5 W cm ^{-2 to} 5 W cm" ² , and a target distance of 5 cm to 15 cm, working The gas pressure is 0.2 Pa to 10 Pa.

9. The method according to claim 1, wherein:

a) in the preparation step (1), the ratio of the number of Cu atoms to the sum of the number of atoms of In and Ga in the prepared CIGS precursor film is 0.5 to 1.0, S 卩 0.5 Cu / (In + Ga) < 1.0;

b) In the preparation step (1), the ratio of the number of Ga atoms to the sum of the numbers of In and Ga atoms in the prepared CIGS precursor film is more than 0, less than 1.0, and S 卩 0 < Ga / (In + Ga) < 1.0.

10. The preparation method according to claim 1 or 8, wherein:

a) The ratio of the number of Cu atoms to the sum of the numbers of In and Ga atoms is 0.70-0.95, S卩0.70 Cu/(In+Ga) 0.95 b) In the preparation step (1), the number of Ga atoms in the prepared CIGS precursor film The ratio to the atomic number of In and Ga is 0.20-0.40, that is, 0.20 Ga/(In+Ga) 0.40.

1 1. The preparation method according to claim 1, wherein:

a) in the preparation step 2, the vacuum refers to the pressure in the reaction vessel 2 Pa;

b) In the preparation step 2, the inert atmosphere is a mixture of one or more of nitrogen, helium, neon and argon, and the certain gas pressure is 5 Pa to 100,000 Pa.