WO2024239651A1 - 一种低温硫等离子体钝化薄膜太阳能电池吸收层及其制备方法与应用 - Google Patents

一种低温硫等离子体钝化薄膜太阳能电池吸收层及其制备方法与应用 Download PDF

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WO2024239651A1
WO2024239651A1 PCT/CN2023/142448 CN2023142448W WO2024239651A1 WO 2024239651 A1 WO2024239651 A1 WO 2024239651A1 CN 2023142448 W CN2023142448 W CN 2023142448W WO 2024239651 A1 WO2024239651 A1 WO 2024239651A1
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solar cell
film solar
low
plasma
absorption layer
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French (fr)
Inventor
李文杰
胡航炜
杨春雷
谭中营
吴莉芸
罗杰
宋世璇
邓立刚
刘旭辉
李伟民
冯叶
钟国华
吴唯
张�杰
邵龑
陈明
宁德
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H10F71/129—Passivating
    • 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
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • 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
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/30—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules comprising thin-film photovoltaic cells
    • 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
    • H10F77/128—Active materials comprising only Group I-II-IV-VI kesterite materials, e.g. Cu2ZnSnSe4 or Cu2ZnSnS4

Definitions

  • the invention belongs to the technical field of solar cells, and in particular relates to a low-temperature sulfur plasma passivated thin-film solar cell absorption layer and a preparation method and application thereof.
  • thin-film solar cells use semiconductor technology to directly convert sunlight into electrical energy.
  • thin-film solar cells with a thickness of only a few microns are semi-transparent and flexible. They can effectively convert solar energy into electrical energy while reducing the amount of materials used, shortening the deposition time and generating electricity in low-light environments.
  • the efficiency of polycrystalline thin-film solar cells is still far from the theoretical SQ limit.
  • This polycrystalline thin-film absorption layer has a large number of defect sites that become recombination sites for photogenerated electrons and holes, accelerating the recombination of photogenerated carriers.
  • Sulfurization of the surface of the absorption layer can reduce surface recombination and improve device efficiency by widening the band gap, and is considered to be an effective passivation method.
  • the thin film of the absorption layer limits the realization of the passivation layer.
  • Traditional sulfurization passivation usually requires high-temperature heat treatment.
  • the sulfur element not only forms a passivation layer on the surface, but also easily enters the interior of the grains to form sulfur-containing quinary phase compounds in the absorption layer films such as CuInGaSe2 and Cu2ZnSnSe4 , which increases the defects inside the grains and reduces the performance of the film layer.
  • the present invention designs a sulfur plasma excitation device and provides a method for passivating the absorption layer of a thin-film solar cell by using low-temperature sulfur plasma.
  • the sulfur plasma excitation device is used to ionize sulfur plasma in a hydrogen sulfide atmosphere to passivate the surface of the absorption layer, including the following steps:
  • a method for preparing a low-temperature sulfur plasma passivated thin-film solar cell absorber layer comprises the following steps:
  • a plasma excitation device including a magnetic field base, a target material, a grounded shell, etc.; a radio frequency power supply is used to provide high-voltage ionized plasma, and the energy of plasma bombarding the target surface is reduced by raising the distance between the target surface and the magnetic field, and the distance between the target surface and the high voltage contact is reduced to increase the probability of plasma generation;
  • Magnetron sputtering is sequentially performed on the substrate to prepare a bottom electrode and co-evaporation is performed to prepare an absorption layer of a thin-film solar cell;
  • the sample prepared in step S2 is placed in a sulfur plasma excitation furnace of a plasma excitation device, a ceramic target is used as a working target, hydrogen sulfide is used as a working gas, and high voltage is applied to generate sulfur plasma to passivate the surface of the sample, so that a passivation layer is formed on the surface of the thin-film solar cell absorption layer of the sample to reduce dark current.
  • step S1 the distance between the target surface and the magnetic field is raised so that the magnetic field strength near the target surface is reduced to 10 Gauss to 20 Gauss.
  • step S1 the distance between the target surface and the high voltage contact is reduced so that the distance between the positive electrode and the grounded shell is reduced to 1 mm to 5 mm.
  • the thickness of the thin-film solar cell absorption layer is 1 ⁇ m to 2.5 ⁇ m.
  • the flow rate of hydrogen sulfide is 3 sccm to 10 sccm
  • the working gas pressure is 0.05 Pa to 1 Pa
  • the plasma excitation power is 40 W to 90 W
  • the passivation treatment time is 1 min to 20 min.
  • the ceramic target material is selected from any one of ZnO, SiO 2 , CdS, and Al 2 O 3 .
  • the size of the ceramic target is The copper back target size is
  • the invention also provides a low-temperature sulfur plasma passivated thin-film solar cell absorption layer prepared by the preparation method, and a surface that inhibits the recombination of electron-hole pairs is formed on the low-temperature sulfur plasma passivated thin-film solar cell absorption layer.
  • the present invention also provides an application of a low-temperature sulfur plasma passivated thin-film solar cell absorption layer prepared by the preparation method in a photovoltaic energy storage device, wherein a buffer layer, an intrinsic zinc oxide layer, a window layer and a second electrode layer are sequentially deposited on the low-temperature sulfur plasma passivated thin-film solar cell absorption layer to obtain a complete photovoltaic energy storage device.
  • the present invention has the following advantages:
  • This method does not require heating, and the sulfurization only occurs on the surface of the nanoscale thin-film solar cell absorption layer, without affecting the interior of the grains, effectively reducing processing time and cost.
  • the passivation layer formed by plasma surface sulfurization reduces the recombination of surface electron-hole pairs by widening the band gap, reducing leakage current and improving the photoelectric conversion efficiency of the device.
  • FIG1 is a schematic diagram of a plasma excitation device provided by the present invention.
  • FIG2 is a SEM image of the copper-zinc-tin-selenium crystalline thin film absorption layer to be treated prepared in Examples 1 to 3 of the present invention.
  • Example 3 is an XPS graph of the surface of the copper-zinc-tin-selenium thin film absorber layer passivated by low-temperature sulfur plasma and after etching 3 nm prepared in Example 1 of the present invention
  • Example 4 is a dark state IV curve of the copper-zinc-tin-selenium thin film absorption layer before and after passivation by low-temperature sulfur plasma prepared in Example 3 of the present invention
  • Example 5 is a comparison diagram of open circuit voltage, short circuit current, fill factor, and efficiency before and after low temperature sulfur plasma passivation of the copper zinc tin selenium thin film absorption layer prepared in Example 3 of the present invention
  • FIG. 6 is a schematic diagram of the process of the present invention.
  • New device By raising the distance between the target surface and the magnetic field, the magnetic field strength near the target surface is reduced to 10 ⁇ 20 Gauss, thereby reducing the energy of plasma bombarding the target surface; at the same time, the distance between the target surface and the high voltage contact is reduced, that is, the distance between the positive electrode and the grounded shell is reduced to 1 ⁇ 5mm, to increase the probability of plasma generation.
  • a 10 ⁇ 10 cm2 soda-lime glass substrate was used as the substrate.
  • the glass substrate was cleaned conventionally using deionized water and a cleaning agent. After the substrate was cleaned using high-purity nitrogen, molybdenum (Mo) was sputtered on its surface by a magnetron sputtering method in an argon atmosphere with a gas pressure of 0.5 Pa as a bottom electrode layer.
  • Mo molybdenum
  • the metal thin film precursor was prepared by co-evaporation.
  • the temperature control programs of copper, zinc, tin, selenium and substrate were respectively increased to 1187 °C, 368 °C, 1181 °C, 245 °C and 150 °C, and then co-evaporated and deposited on the molybdenum back electrode layer of the substrate. In this state, it was maintained for 30 minutes to form a copper-zinc-tin-selenium thin film precursor stacked on the molybdenum back electrode layer. It was then transferred to an annealing furnace, and H 2 Se with a flow rate of 50 sccm for 84 seconds and N 2 with a flow rate of 2.0 slm for 86 seconds were introduced.
  • the temperature was increased to 340 °C for 20 minutes and maintained for 60 minutes. After that, the gas in the cavity was evacuated and H 2 Se with a flow rate of 50 sccm for 14 seconds and N 2 with a flow rate of 2.0 slm for 84 seconds were introduced again. The temperature was increased to 490 °C for 30 minutes and maintained for 10 minutes. After cooling with the furnace, a high-quality CZTSe crystalline absorption layer thin film sample with a thickness of 1.2 ⁇ m was obtained.
  • the CZTSe sample to be treated was transferred to a sulfur plasma excitation furnace, CdS was selected as the target material, the target material and the magnetic field were raised to a magnetic field strength of 20 Gauss near the target material, the distance between the positive electrode and the grounded shell was reduced to 2mm, and the background vacuum value in the plasma excitation furnace was ensured to be at least 8 ⁇ 10 -4 Pa. Then, argon gas with a flow rate of 40sccm was introduced into the plasma excitation furnace, and the working pressure in the sputtering chamber was adjusted to 0.5pa. First, the target surface was pre-cleaned at a power of 75W for 5min, and the gear lever was closed during the process to prevent contamination of the sample.
  • the argon gas was stopped, and hydrogen sulfide gas with a flow rate of 5sccm was introduced.
  • the working gas pressure was adjusted to 0.5pa, and the plasma excitation power was adjusted to 45W.
  • the sulfur plasma was generated to treat the sample surface for 2min, and finally a CZTSe thin film sample with surface passivation treatment was obtained.
  • a buffer layer, an intrinsic zinc oxide layer, a window layer, and a second electrode layer were sequentially made on the CZTSe thin film absorption layer after the passivation treatment to obtain a complete device.
  • Figure 2 is a SEM image of the CZTSe crystalline thin film absorption layer to be treated prepared in Example 1 of the present invention
  • Figure 3 is an XPS image of the copper zinc tin selenium thin film absorption layer passivated by low-temperature sulfur plasma prepared in Example 1 of the present invention before and after treatment and etching of 3nm.
  • a 10 ⁇ 10 cm2 soda-lime glass substrate was used as the substrate.
  • the glass substrate was cleaned conventionally using deionized water and a cleaning agent. After the substrate was cleaned using high-purity nitrogen, molybdenum (Mo) was sputtered on its surface by a magnetron sputtering method in an argon atmosphere with a gas pressure of 0.5 Pa as a bottom electrode layer.
  • Mo molybdenum
  • the metal thin film precursor was prepared by co-evaporation.
  • the temperature control programs of copper, zinc, tin, selenium and substrate were respectively increased to 1187 °C, 368 °C, 1181 °C, 245 °C and 150 °C, and then co-evaporated and deposited on the molybdenum back electrode layer of the substrate. In this state, it was maintained for 30 minutes to form a copper-zinc-tin-selenium thin film precursor stacked on the molybdenum back electrode layer. It was then transferred to an annealing furnace, and H 2 Se with a flow rate of 50 sccm for 84 seconds and N 2 with a flow rate of 2.0 slm for 86 seconds were introduced.
  • the temperature was increased to 340 °C for 20 minutes and maintained for 60 minutes. After that, the gas in the cavity was evacuated and H 2 Se with a flow rate of 50 sccm for 14 seconds and N 2 with a flow rate of 2.0 slm for 84 seconds were introduced again. The temperature was increased to 490 °C for 30 minutes and maintained for 10 minutes. After cooling with the furnace, a high-quality CZTSe crystalline absorption layer thin film sample with a thickness of 1.2 ⁇ m was obtained.
  • the CZTSe sample to be treated was transferred to a sulfur plasma excitation furnace, Al 2 O 3 was selected as the target material, the target material and the magnetic field were raised to a magnetic field strength of 20 Gauss near the target material, the distance between the positive electrode and the ground shell was reduced to 1 mm, and the background vacuum value in the plasma excitation furnace was ensured to be at least 8 ⁇ 10 -4 Pa. Then, 40 sccm of argon gas was introduced into the plasma excitation furnace, and the working pressure in the sputtering chamber was adjusted to 1 Pa. First, the target surface was pre-cleaned at 75 W for 5 minutes, and the gear lever was closed during the process to prevent contamination of the sample.
  • the argon gas was stopped, and the hydrogen sulfide gas was introduced at a flow rate of 5 sccm.
  • the working gas pressure was adjusted to 1 Pa, and the plasma excitation power was adjusted to 45 W.
  • the sulfur plasma was generated to treat the sample surface for 20 minutes, and finally a surface passivated CZTSe thin film sample was obtained.
  • a buffer layer, an intrinsic zinc oxide layer, a window layer, and a second electrode layer were sequentially made on the CZTSe thin film absorption layer after the passivation treatment to obtain a complete device.
  • FIG. 2 is a SEM image of the CZTSe crystalline thin film absorption layer to be treated prepared in Example 2 of the present invention.
  • a 10 ⁇ 10 cm 2 soda-lime glass substrate was used as a substrate.
  • the glass substrate was conventionally cleaned with deionized water and a cleaning agent. After the substrate was cleaned with high-purity nitrogen, molybdenum (Mo) was sputtered on its surface by a magnetron sputtering method in an argon atmosphere with a gas pressure of 0.5 Pa as a bottom electrode layer.
  • Mo molybdenum
  • the metal thin film precursor was prepared by co-evaporation.
  • the temperature control programs of copper, zinc, tin, selenium and substrate were respectively increased to 1187 °C, 368 °C, 1181 °C, 245 °C and 150 °C, and co-evaporated and deposited on the molybdenum back electrode layer of the substrate. In this state, it was maintained for 30 minutes to form a copper-zinc-tin-selenium thin film precursor stacked on the molybdenum back electrode layer. It was then transferred to an annealing furnace, and H 2 Se with a flow rate of 50 sccm for 84 seconds and N 2 with a flow rate of 2.0 slm for 86 seconds were introduced.
  • the temperature was increased to 340 °C for 20 minutes and maintained for 60 minutes. After that, the gas in the cavity was evacuated and H 2 Se with a flow rate of 50 sccm for 14 seconds and N 2 with a flow rate of 2.0 slm for 84 seconds were introduced again. The temperature was increased to 490 °C for 30 minutes and maintained for 10 minutes. After cooling with the furnace, a high-quality CZTSe crystalline absorption layer thin film sample with a thickness of 1.2 ⁇ m was obtained.
  • the CZTSe sample to be treated was transferred to a sulfur plasma excitation furnace, and ZnO was selected as the target.
  • the target and the magnetic field were raised to a magnetic field strength of 20 Gauss near the target, and the distance between the positive electrode and the grounded shell was reduced to 4 mm.
  • the background vacuum value in the plasma excitation furnace was ensured to be at least 8 ⁇ 10 -4 Pa.
  • 40 sccm of argon gas was introduced into the plasma excitation furnace, and the working pressure in the sputtering chamber was adjusted to 0.2 Pa.
  • the target surface was pre-cleaned at 85 W for 5 minutes, and the gear lever was closed during the process to prevent contamination of the sample.
  • the argon gas was stopped, and the hydrogen sulfide gas was introduced at a flow rate of 5 sccm.
  • the working gas pressure was adjusted to 1 Pa, and the plasma excitation power was adjusted to 85 W.
  • the sulfur plasma was generated to treat the sample surface for 3 minutes, and finally a CZTSe thin film sample with surface passivation treatment was obtained.
  • a buffer layer, an intrinsic zinc oxide layer, a window layer, and a second electrode layer were sequentially made on the thin film absorption layer after passivation treatment to obtain a complete device.
  • Figure 2 is a SEM image of the CZTSe crystalline thin film absorption layer to be treated prepared in Example 3 of the present invention
  • Figure 4 is a dark state IV curve of the copper zinc tin selenium thin film absorption layer passivated by low-temperature sulfur plasma prepared in Example 3 of the present invention before and after, and the dark current is effectively reduced after the passivation treatment
  • Figure 5 is a comparison diagram of the open circuit voltage, short circuit current, fill factor and efficiency of the copper zinc tin selenium thin film absorption layer passivated by low-temperature sulfur plasma prepared in Example 3 of the present invention before and after, and after the passivation treatment, the open circuit voltage is increased to 376.8mV, the short circuit current is reduced to 36.2mA/ cm2 , the fill factor is increased to 69.5%, and the efficiency is increased to 8.98%.

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Abstract

本发明公开了一种低温硫等离子体钝化薄膜太阳能电池吸收层及其制备方法与应用，该方法采用新设计的硫等离子体激发装置通过对薄膜太阳能电池的吸收层表面进行硫等离子体的钝化处理来改变表面电子空穴聚集状态，以调整能带排列从而抑制晶界面处电子空穴复合，降低漏电流，最终提高器件效率。本发明提供了一种新的、无需加热就能有效的钝化方法，所制备的CZTSe太阳能电池钝化处理后开路电压提升至376.8mV，短路电流降低至36.2mA/cm 2 ，填充因子提升至69.5%，效率提升至8.98%。

Description

一种低温硫等离子体钝化薄膜太阳能电池吸收层及其制备方法与应用 技术领域
本发明属于太阳能电池技术领域，尤其涉及一种低温硫等离子体钝化薄膜太阳能电池吸收层及其制备方法与应用。
 背景技术
薄膜太阳能电池作为一种新型光伏储能器件，利用半导体技术，直接将太阳光转化为电能。相比于传统的太阳能电池，厚度只有几微米的薄膜太阳能电池具有半透明和柔性的特点，可以有效地将太阳能转化为电能的同时降低材料的使用量，缩短沉积时间并且在弱光环境也能发电。但是由于较低的材料质量，多晶薄膜太阳能电池的效率都仍远远未达到理论SQ极限，这种多晶薄膜吸收层存在大量缺陷位点成为光生电子-空穴的复合位点，加速了光生载流子的复合。
吸收层表面的硫化可以通过带隙加宽来降低表面复合提高器件效率，被认为是一种有效的钝化方法。但是吸收层的薄膜化限制了钝化层的实现，传统硫化法钝化通常需要进行高温热处理，在只有几微米的吸收层材料硫化钝化时，硫元素不只在表面形成钝化层还很容易会进入到晶粒的内部使CuInGaSe 2、Cu 2ZnSnSe 4等吸收层薄膜形成含硫的五元相化合物，增大了晶粒内部的缺陷，降低了膜层的性能。同时高温硫化需要较高的温度和较长的时间，需要能耗较高，对于产业化十分不利，所以寻找一种无需加热、钝化只发生在表面而不影响晶粒内部的硫化方法就十分有必要。
发明内容
为了克服现有技术的不足，本发明设计了一种硫等离子体激发装置并提供了一种低温硫等离子体钝化薄膜太阳能电池吸收层的方法, 通过硫等离子体激发装置在硫化氢气氛中电离产生硫等离子对吸收层表面进行钝化，包括以下步骤：
一种低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，包括以下步骤：
S1、装置搭建：
提供一等离子激发装置，包括磁场基座、靶材、接地外壳利等；用射频电源提供高压电离等离子体，通过架高靶面与磁场的距离以降低等离子轰击靶面的能量，同时降低靶面和高压接触的间距以增加等离子体产生的概率；
S2、样品准备：
在衬底上依次进行磁控溅射制备底电极和共蒸发制备薄膜太阳能电池吸收层；
S3、低温等离子体表面硫化：
将步骤S2制备得到的样品置于等离子激发装置的硫等离子体激发炉中，采用陶瓷靶材为工作靶材，以硫化氢为工作气体，施加高压产生硫等离子体对样品表面进行钝化处理，使样品的薄膜太阳能电池吸收层表面形成钝化层，降低暗电流。
优选的，步骤S1中架高靶面与磁场的距离使得靶面附近磁场强度降低至10高斯~20高斯。
优选的，步骤S1中降低靶面和高压接触的间距使得正极与接地外壳间距降低至1mm ~ 5mm。
优选的，步骤S2中，薄膜太阳能电池吸收层选自CdTe、CuInGaSe 2、Cu 2ZnSn(S,Se) 4、Cu 2Zn xⅡ 1-xSnS 4(Ⅱ=Cd, Ba)中的任一种。
优选的，步骤S2中，薄膜太阳能电池吸收层的厚度为1μm~2.5μm。
优选的，步骤S3中，硫化氢的流量为3sccm ~ 10sccm，工作气压0.05pa ~ 1pa，等离子体激发功率为40W ~ 90W，钝化处理时间为1min ~ 20 min。
优选的，步骤S3中，陶瓷靶材选自ZnO、SiO 2、CdS、Al 2O 3中的任一种。
优选的，陶瓷靶材的尺寸为 铜背靶尺寸为
本发明还提供了该制备方法制备得到的低温硫等离子体钝化薄膜太阳能电池吸收层，低温硫等离子体钝化薄膜太阳能电池吸收层上形成了抑制电子空穴对复合的表面。
本发明还提供了该制备方法制备得到的低温硫等离子体钝化薄膜太阳能电池吸收层在光伏储能器件中的应用，在低温硫等离子体钝化薄膜太阳能电池吸收层上依次沉积缓冲层、本征氧化锌层、窗口层和第二电极层以得到完整的光伏储能器件。
本发明与现有的技术相比，优点在于：
该方法不需要加温，并且硫化只发生在纳米级薄膜太阳能电池吸收层的表面，不会影响晶粒内部，有效地降低了处理时间和成本。等离子体表面硫化形成的钝化层通过带隙加宽来降低表面电子空穴对的复合，降低了漏电流，提高了器件的光电转换效率。
 附图说明
此处的附图被并入说明书中并构成说明书的一部分，示出了符合本发明的实施例，并与说明书一起用于解释本发明的原理，其中：
图1是本发明提供的一种等离子激发装置示意图；
图2是本发明实施例1~3制备的待处理铜锌锡硒结晶薄膜吸收层SEM图；
图3是本发明实施例1制备的低温硫等离子体钝化铜锌锡硒薄膜吸收层前后及刻蚀3nm表面XPS图；
图4是本发明实施例3制备的低温硫等离子体钝化铜锌锡硒薄膜吸收层前后暗态IV曲线；
图5是本发明实施例3制备的低温硫等离子体钝化铜锌锡硒薄膜吸收层前后开路电压、短路电流、填充因数、效率比较图；
图6是本发明的流程示意图。
具体实施方式
下文的公开提供了许多不同的实施方式或例子用来实现本发明的不同结构。为了简化本发明的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本发明。此外，本发明可以在不同例子中重复参考数字和/或参考字母，这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施方式和/或设置之间的关系。
实施例1
新装置：通过架高靶面与磁场的距离使得靶面附近磁场强度降低至10~20高斯，以降低等离子轰击靶面的能量；同时降低靶面和高压接触的间距，即将正极与接地外壳间距降低至1~5mm，以增加等离子体产生的概率。
以10×10cm 2大小的钠钙玻璃为衬底，利用去离子水、清洗剂对玻璃衬底进行常规清洗，利用高纯氮气吹干净衬底后在其表面通过磁控溅射方法在气压0.5Pa的氩气气氛下溅射钼（Mo）作为底电极层。
采用共蒸发制备金属薄膜前驱体，将铜、锌、锡、硒和衬底的控温程序分别升至1187 ℃、368 ℃、1181 ℃、245 ℃和 150 ℃共同蒸发沉积至衬底的钼背电极层上，在此状态下保持30min形成层叠于钼背电极层上的铜锌锡硒薄膜前驱体，之后转移至退火炉中，通入50sccm流量的H 2Se 84秒，通入2.0slm流量的N 286s，20 min升至340 ℃然后保持60min后将腔内气体抽去重新通入14s流量为50 sccm的H 2Se和84s流量为2.0 slm 的N 2，30min升至490℃保持10min后随炉冷却得到厚度为1.2μm高质量待处理的CZTSe结晶吸收层薄膜样品。
将待处理CZTSe样品转移至硫等离子体激发炉内，选择CdS作为靶材，将靶材与磁场架高至靶材附近磁场强度为20高斯，降低正极与接地外壳间距至2mm，等离子体激发炉内，保证等离子体激发炉内本底真空值至少为8×10 -4Pa，再向等离子体激发炉内通入40sccm流量的氩气，调节溅射室内的工作压强为0.5pa，首先以75W功率对靶面进行预清洁处理，时间5min，过程中关闭档把防止污染样品。预清洁处理完成后停止通入氩气，开始通入5sccm流量的硫化氢气体，调节工作气压至0.5pa，将等离子体激发功率调整为45W，开始产生硫等离子处理样品表面，处理时间为2min，最终得到表面钝化处理的CZTSe薄膜样品，在该钝化处理后的CZTSe薄膜吸收层上依次制作缓冲层、本征氧化锌层、窗口层以及第二电极层获得一个完整的器件。
图2是本发明实施例1制备的待处理CZTSe结晶薄膜吸收层SEM图；图3是本发明实施例1制备的低温硫等离子体钝化铜锌锡硒薄膜吸收层处理前后及刻蚀3nm表面的XPS图，钝化处理前表面不存在S的峰，低温硫等离子处理后表面出现S 2p峰表明表面成功被硫等离子体钝化，并且刻蚀3nm后S 2p峰消失表面本发明的低温硫等离子钝化方法只发生在3nm以内的表面而没有发生在晶粒内部。
实施例2
以10×10cm 2大小的钠钙玻璃为衬底，利用去离子水、清洗剂对玻璃衬底进行常规清洗，利用高纯氮气吹干净衬底后在其表面通过磁控溅射方法在气压0.5Pa的氩气气氛下溅射钼（Mo）作为底电极层。
采用共蒸发制备金属薄膜前驱体，将铜、锌、锡、硒和衬底的控温程序分别升至1187 ℃、368 ℃、1181 ℃、245 ℃和 150 ℃共同蒸发沉积至衬底的钼背电极层上，在此状态下保持30min形成层叠于钼背电极层上的铜锌锡硒薄膜前驱体，之后转移至退火炉中，通入50sccm流量的H 2Se 84秒，通入2.0slm流量的N 286s，20 min升至 340 ℃然后保持60min后将腔内气体抽去重新通入14s流量为50 sccm的H 2Se和84s流量为2.0 slm 的N 2，30min升至490℃保持10min后随炉冷却得到厚度为1.2μm高质量待处理的CZTSe结晶吸收层薄膜样品。
将待处理CZTSe样品转移至硫等离子体激发炉内，选择Al 2O 3作为靶材，将靶材与磁场架高至靶材附近磁场强度为20高斯，降低正极与接地外壳间距至1mm，等离子体激发炉内，保证等离子体激发炉内本底真空值至少为8×10 -4Pa，再向等离子体激发炉内通入40sccm流量的氩气，调节溅射室内的工作压强为1pa，首先以75W功率对靶面进行预清洁处理，时间5min，过程中关闭档把防止污染样品。预清洁处理完成后停止通入氩气，开始通入5sccm流量的硫化氢气体，调节工作气压至1pa，将等离子体激发功率调整为45W，开始产生硫等离子处理样品表面，处理时间为20min，最终得到表面钝化处理的CZTSe薄膜样品，在钝化处理后的CZTSe薄膜吸收层上依次制作缓冲层、本征氧化锌层、窗口层以及第二电极层获得一个完整的器件。
图2是本发明实施例2制备的待处理CZTSe结晶薄膜吸收层SEM图。
实施例3
以10×10cm 2大小的钠钙玻璃为衬底，利用去离子水、清洗剂对玻璃衬底进行常规清洗，利用高纯氮气吹干净所述衬底后在其表面通过磁控溅射方法在气压0.5Pa的氩气气氛下溅射钼（Mo）作为底电极层。
采用共蒸发制备金属薄膜前驱体，将铜、锌、锡、硒和衬底的控温程序分别升至1187 ℃、368 ℃、1181 ℃、245 ℃和 150 ℃共同蒸发沉积至衬底的钼背电极层上，在此状态下保持30min形成层叠于钼背电极层上的铜锌锡硒薄膜前驱体，之后转移至退火炉中，通入50sccm流量的H 2Se 84秒，通入2.0slm流量的N 286s，20 min 升至 340 ℃然后保持60min后将腔内气体抽去重新通入14s流量为50 sccm的H 2Se和84s流量为2.0 slm 的N 2，30min升至490℃保持10min后随炉冷却得到厚度为1.2μm高质量待处理的CZTSe结晶吸收层薄膜样品。
将待处理CZTSe样品转移至硫等离子体激发炉内，选择ZnO作为靶材，将靶材与磁场架高至靶材附近磁场强度为20高斯，降低正极与接地外壳间距至4mm，等离子体激发炉内，保证等离子体激发炉内本底真空值至少为8×10 -4Pa，再向等离子体激发炉内通入40sccm流量的氩气，调节溅射室内的工作压强为0.2pa，首先以85W功率对靶面进行预清洁处理，时间5min，过程中关闭档把防止污染样品。预清洁处理完成后停止通入氩气，开始通入5sccm流量的硫化氢气体，调节工作气压至1pa，将等离子体激发功率调整为85W，开始产生硫等离子处理样品表面，处理时间为3min，最终得到表面钝化处理的CZTSe薄膜样品，在钝化处理后的薄膜吸收层上依次制作缓冲层、本征氧化锌层、窗口层以及第二电极层获得一个完整的器件。
图2是本发明实施例3制备的待处理CZTSe结晶薄膜吸收层SEM图；图4是本发明实施例3制备的低温硫等离子体钝化铜锌锡硒薄膜吸收层前后暗态IV曲线，钝化处理后暗电流有效减小；图5是发明实施例3制备的低温硫等离子体钝化铜锌锡硒薄膜吸收层前后开路电压、短路电流、填充因数、效率比较图，钝化处理后开路电压提升至376.8mV，短路电流降低至36.2mA/cm 2，填充因子提升至69.5%，效率提升至8.98%。
本领域技术人员在考虑说明书及实践这里的发明后，将容易想到本发明的其它实施方案。本发明旨在涵盖本发明的任何变型、用途或者适应性变化，这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的，本发明的真正范围和精神由权利要求指出。
应当理解的是，本发明并不局限于上面已经描述并在附图中示出的精确结构，并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。

Claims (10)

  1. 一种低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，包括以下步骤：
    S1、装置搭建：
    提供一等离子激发装置，包括磁场基座、靶材、接地外壳利等；用射频电源提供高压电离等离子体，通过架高靶面与磁场的距离以降低等离子轰击靶面的能量，同时降低靶面和高压接触的间距以增加等离子体产生的概率；
    S2、样品准备：
    在衬底上依次进行磁控溅射制备底电极和共蒸发制备薄膜太阳能电池吸收层；
    S3、低温等离子体表面硫化：
    将步骤S2制备得到的样品置于所述等离子激发装置的硫等离子体激发炉中，采用陶瓷靶材为工作靶材，以硫化氢为工作气体，施加高压产生硫等离子体对所述样品表面进行钝化处理，使所述样品的薄膜太阳能电池吸收层表面形成钝化层，降低暗电流。
  2. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，步骤S1中架高靶面与磁场的距离使得靶面附近磁场强度降低至10高斯~20高斯。
  3. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，步骤S1中降低靶面和高压接触的间距使得正极与接地外壳间距降低至1mm ~ 5mm。
  4. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，步骤S2中，所述薄膜太阳能电池吸收层选自CdTe、CuInGaSe 2 、Cu 2 ZnSn(S,Se) 4 、Cu 2 Zn x Ⅱ 1-x SnS 4 (Ⅱ=Cd, Ba)中的任一种。
  5. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，步骤S2中，所述薄膜太阳能电池吸收层的厚度为1μm~2.5μm。
  6. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，步骤S3中，所述硫化氢的流量为3sccm ~ 10sccm，工作气压0.05pa ~ 1pa，等离子体激发功率为40W ~ 90W，所述钝化处理时间为1min ~ 20 min。
  7. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，步骤S3中，所述陶瓷靶材选自ZnO、SiO 2 、CdS、Al 2 O 3 中的任一种。
  8. 根据权利要求1所述的低温硫等离子体钝化薄膜太阳能电池吸收层的制备方法，其特征在于，所述陶瓷靶材的尺寸为 铜背靶尺寸为
  9. 权利要求1~8任一项所述的制备方法制备得到的低温硫等离子体钝化薄膜太阳能电池吸收层，其特征在于，所述低温硫等离子体钝化薄膜太阳能电池吸收层上形成了抑制电子空穴对复合的表面。
  10. 权利要求1~8任一项所述的制备方法制备得到的低温硫等离子体钝化薄膜太阳能电池吸收层在光伏储能器件中的应用，其特征在于，在所述低温硫等离子体钝化薄膜太阳能电池吸收层上依次沉积缓冲层、本征氧化锌层、窗口层和第二电极层以得到完整的光伏储能器件。
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