WO2024060423A1 - Cigs太阳能电池表面改性方法、装置及cigs太阳能电池 - Google Patents

Cigs太阳能电池表面改性方法、装置及cigs太阳能电池 Download PDF

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WO2024060423A1
WO2024060423A1 PCT/CN2022/138194 CN2022138194W WO2024060423A1 WO 2024060423 A1 WO2024060423 A1 WO 2024060423A1 CN 2022138194 W CN2022138194 W CN 2022138194W WO 2024060423 A1 WO2024060423 A1 WO 2024060423A1
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microwave plasma
cigs
solar cell
surface modification
microwave
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French (fr)
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唐玮
李伟民
苑欣业
俞深
王赛强
李松
赵晨晨
祁同庆
马明
宁德
杨春雷
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5826—Treatment with charged particles
    • C23C14/5833—Ion beam bombardment
    • 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
    • H10F10/167—Photovoltaic cells having only PN heterojunction potential barriers comprising Group I-III-VI materials, e.g. CdS/CuInSe2 [CIS] heterojunction 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
    • 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
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/22—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using physical deposition, e.g. vacuum deposition or sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3436—Deposited materials, e.g. layers characterised by the chemical composition being chalcogenide semiconductor materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/38—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by treatments done after the formation of the materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • This application relates to the technical field of thin film solar cells, and in particular to a CIGS solar cell surface modification method, device and CIGS solar cell.
  • CIGS solar cells are one of the most promising solar cells at present. They have the advantages of short energy recovery cycle, high power generation, good power generation stability, strong light absorption capacity, high conversion efficiency, and long power generation time during the day.
  • high-efficiency CIGS solar cell surface modification devices are usually fabricated at high substrate temperatures above 550°C. Manufacturing CIGS solar cell surface modification devices at temperatures below 500°C has huge advantages, reducing energy consumption and equipment requirements under high temperature conditions, thereby reducing the cost of CIGS solar cell surface modification devices and components.
  • low-temperature CIGS fabrication processes can be applied to certain substrates, such as flexible polyimide (PI) substrates, to obtain lightweight CIGS solar cell surface modification devices for building integrated photovoltaics and space applications.
  • PI flexible polyimide
  • CIGS thin films were prepared using a three-step co-evaporation method of copper, indium, gallium, selenium and other elements, which can well control the sample composition.
  • a Cu-Se phase will easily form on the surface, causing the reaction to be incomplete and impurity levels to appear, affecting the efficiency of the battery.
  • the Ga content will be high near the Mo back electrode and low near the surface, resulting in a large band gap at the bottom and a small band gap at the top, causing the surface to have a shielding effect on solar energy of some frequencies.
  • exposure to moisture in the air and during the vacuum process can also cause surface contamination.
  • One of the purposes of this application is to provide a modification method for a CIGS solar cell surface modification device, which includes the following steps:
  • Preparing the CIGS film on the CIGS absorption layer includes: in the first step, evaporating about 85-90% of In and Ga on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C to form (In , Ga) 2 Se 3 prefabricated layer; in the second step, open the baffle of the Cu source and evaporate only Cu to form a CIGS crystal; keep the substrate temperature the same as in the second step, evaporate the remaining 10% of In and Ga, and keep The evaporation time is 15-20 minutes, allowing it to react with the excess Cu in the second step, eventually forming a slightly Cu-poor CIGS film;
  • the microwave power source to ionize the inert gas in the microwave plasma generation chamber and generate microwave plasma.
  • the magnetic field generated by the deflection coil leads the microwave plasma from the microwave plasma generation chamber to the vacuum chamber, and the microwave plasma is directed towards the vacuum chamber.
  • the CIGS film in the vacuum chamber undergoes surface modification treatment, and the microwave plasma removes CuSe on the surface of the CIGS film; 2) Free Se absorbs electrons in the microwave plasma and transforms into Se ions ;
  • a Ni/Al/Ni gate electrode was deposited on the i-ZnO and AZO window layers.
  • the method further includes the following steps: turning on a high-voltage power supply between the microwave plasma generation chamber and the sample rack, and loading high voltage between the microwave plasma generation chamber and the sample rack.
  • NaF and KF can be evaporated on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C, or after completing the third step, another evaporation layer can be evaporated at a temperature of 300°C.
  • Layer NaF or KF layer can be evaporated on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C, or after completing the third step, another evaporation layer can be evaporated at a temperature of 300°C.
  • Layer NaF or KF layer can be evaporated on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C, or after completing the third step, another evaporation layer can be evaporated at a temperature of 300°C.
  • Layer NaF or KF layer can be evaporated on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C, or after completing the third step, another evaporation layer can be evaporated at a temperature of 300°C.
  • the second object of the present application is to provide a modification device of the CIGS solar cell surface modification method, comprising a vacuum chamber, a deflection coil arranged inside and outside the vacuum chamber, and a microwave plasma unit connected to the vacuum chamber, wherein the microwave plasma unit comprises a microwave power source, a microwave plasma generating chamber connected to the microwave power source, and a magnetic field coil arranged around the microwave plasma generating chamber, wherein the microwave plasma generating chamber is connected to the vacuum chamber, and the CIGS film is also arranged in the vacuum chamber;
  • the microwave power source to ionize the inert gas in the microwave plasma generation chamber and generate microwave plasma.
  • the magnetic field generated by the deflection coil leads the microwave plasma from the microwave plasma generation chamber to the In a vacuum chamber, the microwave plasma performs surface modification treatment on the CIGS film, and the microwave plasma removes CuSe on the surface of the CIGS film; free Se absorbs electrons in the microwave plasma, Transformed into Se ions;
  • a sample holder is also provided at the bottom of the vacuum chamber, and the CIGS film is fixed on the sample holder.
  • the magnetic field of the magnetic field coil is adjustable, and the magnetic field generated by the magnetic field coil is adjusted to match the microwave frequency of the microwave plasma.
  • a high-voltage power supply is loaded between the microwave plasma generation chamber and the sample holder.
  • the high-voltage power supply can enhance the beam intensity of the microwave plasma at a high voltage.
  • the high-voltage power supply voltage loaded between the microwave plasma generation chamber and the sample holder is between 200V and 1000V, the microwave power of the microwave plasma is 45W, and the gas flow rate is 5sccm.
  • the working pressure is 2 ⁇ 10 -3 p.
  • the vacuum chamber is also connected to a mechanical pump, and the mechanical pump can evacuate the vacuum chamber.
  • the third purpose of this application is to provide a CIGS solar cell, which includes a soda-lime glass substrate, a Mo back electrode, a CIGS film, a CdS buffer layer, an i-ZnO and AZO window layer and a Ni-Al-Ni gate that are stacked in sequence. electrode, the surface of the CIGS film is modified by microwave plasma.
  • the microwave power source is turned on to ionize the inert gas in the microwave plasma generation chamber and generate microwave plasma.
  • the magnetic field generated by the deflection coil deflects the microwave Plasma is led from the microwave plasma generation chamber to the vacuum chamber, the microwave plasma performs surface modification treatment on the CIGS film in the vacuum chamber, and the microwave plasma cleans the surface of the CIGS film CuSe on the surface of the CIGS film; 2) Free Se absorbs electrons in the microwave plasma and transforms into Se ions, which can not only remove the Cu-Se phase on the surface, but also weaken the unevenness of Ga in the CIGS film and avoid The shielding effect on solar energy appears, thereby achieving the purpose of material surface modification and obtaining higher photoelectric conversion efficiency.
  • the above modification methods and devices avoid surface contamination caused by moisture in a closed and non-vacuum process.
  • Figure 1 is a step flow chart of the CIGS solar cell surface modification method provided by the embodiment of the present application.
  • Figure 2 is a schematic structural diagram of a CIGS solar cell surface modification device provided by an embodiment of the present application.
  • Figure 3 is a schematic structural diagram of a CIGS solar cell provided in an embodiment of the present application.
  • first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • plurality means two or more than two, unless otherwise explicitly and specifically limited.
  • Figure 1 is a step flow chart of a CIGS solar cell surface modification method provided by an embodiment of the present application, including the following steps:
  • Step S110 Deposit the Mo back electrode on the soda-lime glass substrate.
  • Step S120 depositing the CIGS absorption layer on the Mo back electrode.
  • Step S130 Preparing the CIGS film on the CIGS absorption layer, including: the first step, evaporating about 85-90% of In and Ga on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C, Form a (In,Ga) 2 Se 3 prefabricated layer; in the second step, open the baffle of the Cu source and evaporate only Cu to form a CIGS crystal; keep the substrate temperature the same as in the second step and evaporate the remaining 10% of In and Ga, keep the evaporation time at 15-20 minutes, so that it can react with the excess Cu in the second step, eventually forming a slightly Cu-poor CIGS film.
  • the CIGS thin film provided in this application is prepared by an improved three-step co-evaporation method, including: the first step is to evaporate 85% of the CIGS absorption layer surface at a substrate temperature of 360-390°C. -About 90% In and Ga to form a (In,Ga) 2 Se 3 prefabricated layer.
  • the second step open the baffle of the Cu source and evaporate only Cu to form a CIGS crystal.
  • the third step keep the substrate temperature consistent with the first
  • the second step is the same, evaporate the remaining 10% of In and Ga, keep the evaporation time at 15-20 minutes, and allow it to react with the excess Cu in the second step, eventually forming a slightly Cu-poor CIGS film.
  • NaF and KF can be evaporated on the surface of the CIGS absorption layer at a substrate temperature of 360-390°C, or after completing the third step, evaporate at a temperature of about 300°C.
  • alkali metal fluorides NaF and KF can be used for treatment to reduce the bandgap width, reduce crystal interface and internal crystal defects, and improve photoelectric conversion efficiency.
  • the entire experimental process was carried out in an atmosphere with a sufficient amount of Se.
  • the CIGS film was plasma annealed and reverse sputtered with ionized H 2 S plasma on the surface to avoid surface oxidation and reduce the passivation effect on the surface. Grain boundary recombination increases the p-type concentration in the CIGS film.
  • CIGS films are deposited via a modified three-step co-evaporation process that incorporates an additional copper-rich phase deposition after the second step, enabling low-temperature growth even in the absence of post-deposition alkali metal element treatments.
  • the efficiency of CIGS solar cells deposited at 460°C is comparable to that deposited at a high temperature of 540°C. It solves the problems of poor crystallization properties of CIGS films caused by too low substrate temperature, excessively small crystal grains, and increased recombination probability of photogenerated carriers, resulting in reduced photoelectric conversion efficiency of the battery.
  • CIGS thin films are prepared using a three-step co-evaporation method of copper, indium, gallium, selenium and other elements.
  • the sample composition can be well controlled, if the growth rate of copper cannot be controlled during the second step of copper growth, It is easy to form a Cu-Se phase on the surface, causing the reaction to be incomplete and impurity levels to appear, affecting the efficiency of the battery.
  • the Ga content will be high near the Mo back electrode and low near the surface, resulting in a large band gap at the bottom and a small band gap at the top, causing the surface to have a shielding effect on solar energy of some frequencies.
  • Step S140 Turn on the microwave power source to ionize the inert gas in the microwave plasma generating chamber and generate microwave plasma.
  • the magnetic field generated by the deflection coil draws the microwave plasma from the microwave plasma generating chamber to the vacuum chamber.
  • the microwave plasma also performs surface modification on the CIGS film in the vacuum chamber.
  • the microwave plasma removes CuSe on the surface of the CIGS film. 2) Free Se absorbs electrons in the microwave plasma and is converted into Se ions.
  • the surface treatment of the CIGS film by microwave plasma in this application has the following effects: 1) The microwave plasma produces a reverse sputtering effect on the surface of the CIGS film, which can remove CuSe on the surface of the CIGS film; 2) Free Se Absorb the electrons in the microwave plasma and convert them into Se ions.
  • Step S150 Prepare the i-ZnO and AZO window layers on the surface-modified CIGS film.
  • Step S160 Deposit a Ni/Al/Ni gate electrode on the i-ZnO and AZO window layers.
  • the method further includes the following steps: turning on the high-voltage power supply between the microwave plasma generation chamber and the sample rack, and loading high voltage between the microwave plasma generation chamber and the sample rack,
  • the high-voltage power supply can enhance the beam intensity of the microwave plasma at high voltage.
  • the CIGS solar cell surface modification method uses microwave plasma to perform surface modification treatment on the CIGS film, and the microwave plasma removes CuSe on the surface of the CIGS film on the surface of the CIGS film; 2) free state
  • the Se absorbs the electrons in the microwave plasma and transforms into Se ions, which can not only remove the Cu-Se phase on the surface, but also weaken the Ga unevenness in the CIGS film and avoid the film's shielding effect on solar energy, thus reaching the surface of the material.
  • the purpose of modification is to obtain higher photoelectric conversion efficiency.
  • the above modification method avoids surface contamination caused by moisture during the closed and non-vacuum process.
  • FIG 2 is a schematic structural diagram of a CIGS solar cell surface modification device provided by an embodiment of the present application, including: a vacuum chamber 110, a deflection coil 120 disposed inside and outside the vacuum chamber 110, and the A microwave plasma unit 130 is connected to the vacuum chamber 110.
  • the microwave plasma unit 130 includes a microwave power source 131, a microwave plasma generation chamber 132 connected to the microwave power source 131, and a microwave plasma generation chamber 132 arranged around it.
  • the magnetic field coil 133, the microwave plasma generation chamber 132 is connected to the vacuum chamber 110, and a CIGS film is also installed in the vacuum chamber.
  • deflection coil 120 which surrounds the inside and outside of the vacuum chamber; or deflection coils are provided both inside and outside the vacuum chamber.
  • the microwave power source 131 is turned on to ionize the inert gas in the microwave plasma generating chamber 132 and generate microwave plasma.
  • the magnetic field generated by the deflection coil 120 draws the microwave plasma from the microwave plasma generating chamber 132 to the vacuum chamber 110.
  • the microwave plasma performs surface modification on the CIGS film 100 in the vacuum chamber 110.
  • the microwave plasma generates a reverse sputtering effect on the film surface, which can remove CuSe on the surface of the CIGS film.
  • the free Se absorbs electrons in the microwave plasma and is converted into Se ions. Since the microwave plasma acts on the surface of the CIGS film, the temperature of the CIGS film rises.
  • a sample holder 140 is also provided at the bottom of the vacuum chamber 110, and the CIGS film 100 is fixed on the sample holder.
  • the magnetic field of the magnetic field coil 133 is adjustable, and the magnetic field generated by the magnetic field coil 133 is adjusted to match the microwave frequency of the microwave plasma.
  • a high-voltage power supply (not shown) is loaded between the microwave plasma generation chamber 132 and the sample holder 140 .
  • the high-voltage power supply can enhance the beam intensity of the microwave plasma at high voltage. .
  • the high-voltage power supply voltage loaded between the microwave plasma generation chamber and the sample holder is between 200V and 1000V, the microwave power of the microwave plasma is 45W, and the gas flow rate is 5sccm.
  • the working pressure is 2 ⁇ 10 -3 p.
  • the vacuum chamber 110 is also connected to a mechanical pump 150, and the mechanical pump 110 can evacuate the vacuum chamber.
  • the CIGS solar cell surface modification device uses microwave plasma to perform surface modification treatment on the CIGS film.
  • the microwave plasma removes CuSe on the surface of the CIGS film on the surface of the CIGS film; 2) free state
  • the Se absorbs the electrons in the microwave plasma and transforms into Se ions, which can not only remove the Cu-Se phase on the surface, but also weaken the Ga unevenness in the CIGS film and avoid the film's shielding effect on solar energy, thus reaching the surface of the material.
  • the purpose of modification is to obtain higher photoelectric conversion efficiency.
  • the above-mentioned modification device avoids surface contamination caused by moisture during the closed and non-vacuum process.
  • the CIGS solar cell provided in the above embodiment of the present application includes a soda-lime glass substrate 11, a Mo back electrode 12, a CIGS film 13, a CdS buffer layer 14, i-ZnO and an AZO window layer 15 that are stacked in sequence. and Ni-Al-Ni gate electrode 16.
  • the Mo back electrode 120 includes a double-layer Mo film
  • the double-layer Mo film includes a loose layer and a dense layer
  • the thickness of the double-layer Mo film is 500-1000 nm.
  • the CIGS film 13 includes 88 at.% GGI (Ga/([Ga]+[In]) and 35 at.% CIG (Cu/([Ga]+[In])), The thickness of the CIGS film 13 is 1.8-3 ⁇ m.
  • the CdS buffer layer is an n-type CdS buffer layer with a thickness of 30-80 nm.
  • the thickness of i-ZnO is 50-100 nm, and the thickness of ZnO:Al is 100-300 nm.
  • the Ni-Al-Ni gate electrode includes a first layer of Ni electrode, an Al electrode evaporated on the first layer of Ni electrode, and a second layer of Ni covering the Al electrode. Electrode, the thickness of the first layer Ni electrode is 50-1000 ⁇ , the thickness of the Al electrode is 5-10 ⁇ m, and the thickness of the second layer Ni electrode is 50-1000 ⁇ .
  • the CIGS solar cell provided in the above embodiments of the present application generates plasma by ionizing inert gas, and acts on the surface of the CIGS film of copper indium gallium selenide.
  • the CIGS film is subjected to plasma annealing and reverse sputtering, which can not only remove The Cu-Se phase on the surface can also further anneal the film to weaken the uneven condition of Ga, thereby achieving the purpose of surface modification of the material.
  • alkali metal fluorides NaF and KF can be used for treatment at the beginning of the first step and after the end of the third step to reduce the bandgap width and reduce defects at the crystal interface and within the crystal. Improve photoelectric conversion efficiency.
  • CdS as a buffer layer and PN junction forming layer on the surface of the CIGS film.
  • CdSO 4 as the cadmium source
  • thiourea as the sulfur precursor
  • NH 3 •H 2 0 as the buffer
  • a CdS film was prepared on the surface of the CIGS film using the water bath method. After the reaction, it was annealed at 160°C.
  • I-ZnO Indium Zinc Oxide
  • O 2 Ar-doped zinc oxide
  • 2 sccm the initial sputtering power is 120W, and subsequently increased to 220W.
  • the reaction gases used in AZO are Ar and H 2 , the flow rate of Ar is 200 sccm, and the flow rate of H 2 is 2 sccm. It needs to be kept at 160°C for 15 minutes, and the sputtering power is 750W.
  • the target materials used are Ni and Al, where the Ni layer thickness is 1500 ⁇ and the Al thickness is 100000 ⁇ .
  • the gate electrode is obtained and the CIGS solar cell preparation process is completed.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

一种CIGS太阳能电池表面改性方法及改性装置，该方法包括开启微波功率源(131)，使得微波等离子体产生室(132)的惰性气体电离并产生微波等离子体，偏转线圈(120)产生的磁场将微波等离子体从微波等离子体产生室(132)引出至真空室(110)，并对真空室(110)内的CIGS薄膜(100)进行表面改性处理，不仅可以去除表面的Cu-Se相，还可以减弱CIGS薄膜(100)中Ga的不均匀状况，避免薄膜出现对太阳能的屏蔽作用，从而达到材料表面改性的目的，以获得了更高光电转换效率。

Description

CIGS太阳能电池表面改性方法、装置及CIGS太阳能电池 技术领域
本申请涉及薄膜太阳能电池技术领域，特别涉及一种CIGS太阳能电池表面改性方法、装置及CIGS太阳能电池。
 背景技术
CIGS太阳能电池是目前最有前景的太阳能电池之一，具有能源回收周期短，发电量高，发电稳定性好，光吸收能力强，转换效率高，白天发电时间长等优点。然而，高效CIGS太阳能电池表面改性装置通常是在550℃以上的高基板温度下制备的。在低于500℃的温度下制造CIGS太阳能电池表面改性装置具有巨大的优势，降低了高温条件下的能源消耗和设备要求，从而降低了CIGS太阳能电池表面改性装置和组件的成本。此外，低温CIGS制造工艺可以应用于某些基板，例如柔性聚酰亚胺(PI)基板，以获得用于构建集成光伏和空间应用的轻型CIGS太阳能电池表面改性装置。先前的研究表明，在低于450℃的温度下沉积的CIGS的效率可以与在高于550℃的高温下沉积的CIGS的效率相媲美。最近，Tiwari和他的同事们报道了在450℃沉积的聚酰亚胺基板上的20.8%的新记录效率，这归功于他们将碱元素掺入CIGS的精心策略。
利用铜、铟、镓、硒等元素的三步法共蒸发制备了CIGS薄膜，可以很好地控制样品成分。但是在第二步铜的生长过程中，如果不能掌握铜的生长速率，容易使表面形成Cu-Se相，使得反应不够完全，出现杂质能级，影响电池的效率。此外，会使得Ga含量在靠近Mo背电极部分含量高，靠近表面部分含量低的特征，导致底部的带隙大，顶部的带隙小，致使表面对部分频率的太阳能有屏蔽作用。且暴露在空气中和真空过程中的湿气也会造成表面污染。
 技术问题
鉴于此，有必要针对现有技术中存在的缺陷提供一种可对CIGS太阳能电池表面进行改性的CIGS太阳能电池表面改性装置及其制备方法。
 技术解决方案
为解决上述问题，本申请采用下述技术方案：
本申请目的之一，提供了一种CIGS太阳能电池表面改性装置的改性方法，包括下述步骤：
在所述钠钙玻璃衬底上沉积所述Mo背电极；
在所述Mo背电极上沉积所述CIGS吸收层；
在所述CIGS吸收层上制备所述CIGS薄膜，包括：第一步，在360-390℃衬底温度下，在所述CIGS吸收层表面蒸发85-90%左右的In和Ga，形成(In,Ga) 2Se 3预制层；第二步，打开Cu源的挡板，只蒸发Cu，形成CIGS结晶；保持衬底温度与第二步相同，蒸发剩下的10%的In和Ga，保持蒸发的时间在15-20分钟，使其与第二步中过量的Cu反应，最终生成略贫Cu的CIGS薄膜；
开启所述微波功率源，使得所述微波等离子体产生室的惰性气体电离并产生微波等离子体，偏转线圈产生的磁场将微波等离子体从微波等离子体产生室引出至真空室，微波等离子体并对真空室内的所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子；
在表面改性的所述CIGS薄膜上制备所述i-ZnO和AZO窗口层；
在所述i-ZnO和AZO窗口层上沉积Ni/Al/Ni 栅电极。
在其中一些实施例中，还包括下述步骤：开启所述微波等离子体产生室与所述样品架之间的高压电源，在所述微波等离子体产生室与所述样品架之间加载高压。
在所述第一步中，在360-390℃衬底温度下，在所述CIGS吸收层表面还可以蒸发有NaF、KF或者在完成第三步后，于300℃温度下，再蒸镀一层NaF或KF层。
本申请目的之二，提供了一种所述的CIGS太阳能电池表面改性方法的改性装置，包括真空室、设置于所述真空室内及外侧的偏转线圈、与所述真空室连接的微波等离子体单元，所述微波等离子体单元包括微波功率源、与所述微波功率源连接的微波等离子体产生室及围绕所述微波等离子体产生室设置的磁场线圈，所述微波等离子体产生室与所述真空室连接，所述真空室内还设置有所述CIGS薄膜；
开启所述微波功率源，使得所述微波等离子体产生室的惰性气体电离并产生微波等离子体，所述偏转线圈产生的磁场将所述微波等离子体从所述微波等离子体产生室引出至所述真空室，所述微波等离子体对所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；游离态的Se吸收微波等离子体中的电子，转变成Se离子；
在其中一些实施例中，所述真空室的底部还设置有样品架，所述CIGS薄膜固定于所述样品架上。
在其中一些实施例中，所述磁场线圈的磁场可调节，通过调节所述磁场线圈产生的磁场与所述微波等离子体的微波频率相匹配。
在其中一些实施例中，所述微波等离子体产生室与所述样品架之间还加载有高压电源，所述高压电源可高压加强所述微波等离子体的束流强度。
在其中一些实施例中，所述磁场线圈产生的磁场强度B与所述微波等离子体的微波频率f，满足关系2πf＝eB/m。
在其中一些实施例中，加载在所述微波等离子体产生室与所述样品架之间的高压电源电压在200V～1000V之间，所述微波等离子体的微波功率为45W，气体流量为5sccm，工作压强为2×10 -3p。
在其中一些实施例中，所述真空室还连接有机械泵，所述机械泵可对所述真空室抽真空处理。
本申请目的之三，提供了一种CIGS太阳能电池，包括依次层叠设置的钠钙玻璃衬底、Mo背电极、CIGS薄膜、CdS缓冲层、i-ZnO和AZO窗口层及Ni-Al-Ni栅电极，所述CIGS薄膜的表面经微波等离子体改性处理。
 有益效果
本申请采用上述技术方案，其有益效果如下：
本申请提供的CIGS太阳能电池表面改性方法及装置，开启所述微波功率源，使得所述微波等离子体产生室的惰性气体电离并产生微波等离子体，所述偏转线圈产生的磁场将所述微波等离子体从所述微波等离子体产生室引出至所述真空室，所述微波等离子体对所述真空室内的所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子，不仅可以去除表面的Cu-Se相，还可以减弱CIGS薄膜中Ga的不均匀状况，避免薄膜出现对太阳能的屏蔽作用，从而达到材料表面改性的目的，以获得了更高光电转换效率。此外，上述改性方法及装置均在密闭及非真空过程中的避免由于湿气造成的表面污染。
 附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例提供的CIGS太阳能电池表面改性方法的步骤流程图。
图2为本申请实施例提供的CIGS太阳能电池表面改性装置的结构示意图。
图3为本申请实施例提供的CIGS太阳能电池的结构示意图。
 本发明的实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。
在本申请的描述中，需要理解的是，术语“上”、“下”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。
请参阅图1，为本申请一实施例提供的CIGS太阳能电池表面改性方法的步骤流程图，包括下述步骤：
步骤S110：在所述钠钙玻璃衬底上沉积所述Mo背电极。
步骤S120：在所述Mo背电极上沉积所述CIGS吸收层。
步骤S130：在所述CIGS吸收层上制备所述CIGS薄膜，包括：第一步，在360-390℃衬底温度下，在所述CIGS吸收层表面蒸发85-90%左右的In和Ga，形成(In,Ga) 2Se 3预制层；第二步，打开Cu源的挡板，只蒸发Cu，形成CIGS结晶；保持衬底温度与第二步相同，蒸发剩下的10%的In和Ga，保持蒸发的时间在15-20分钟，使其与第二步中过量的Cu反应，最终生成略贫Cu的CIGS薄膜。
在本实施例中，本申请提供的所述CIGS薄膜由改进的三步法共蒸发制备得到，包括：第一步，在360-390℃衬底温度下，在所述CIGS吸收层表面蒸发85-90%左右的In和Ga，形成(In,Ga) 2Se 3预制层，第二步，打开Cu源的挡板，只蒸发Cu，形成CIGS结晶，第三步，保持衬底温度与第二步相同，蒸发剩下的10%的In和Ga，保持蒸发的时间在15-20分钟，使其与第二步中过量的Cu反应，最终生成略贫Cu的CIGS薄膜。
进一步地，在第一步中，在360-390℃衬底温度下，在所述CIGS吸收层表面还可以蒸发有NaF、KF或者在完成第三步后，于300℃左右温度，再蒸镀一层NaF或KF层。
可以理解，在第一步开始同时以及第三步结束后，可利用碱金属氟化物NaF、KF进行处理，以减小禁带宽度减少晶界面与晶体内部缺陷，提高光电转化效率。
整个实验过程都是在足量的Se的气氛中进行，在表面用电离的H 2S等离子体对CIGS薄膜进行等离子体退火和反溅射，避免了表面氧化，表面的钝化效果减少了晶界复合，提高了CIGS薄膜中的p型浓度。
通过改进的三步法共蒸发工艺来沉积CIGS薄膜，该工艺在第二步之后加入了额外的富铜相沉积，即使在没有沉积后碱金属元素处理的条件下，这种工艺也能够低温生长具有良好结晶度的大CIGS晶粒。在460℃下沉积的CIGS太阳能电池的效率与在540℃高温下沉积的效率相当。解决了衬底温度过低导致的CIGS薄膜的结晶性能变差，晶粒过小，光生载流子复合几率增大，从而导致的电池的光电转换效率降低等问题。
但是利用铜、铟、镓、硒等元素的三步法共蒸发制备了CIGS薄膜，尽管可以很好地控制样品成分，但是在第二步铜的生长过程中，如果不能掌握铜的生长速率，容易使表面形成Cu-Se相，使得反应不够完全，出现杂质能级，影响电池的效率。此外，会使得Ga含量在靠近Mo背电极部分含量高，靠近表面部分含量低的特征，导致底部的带隙大，顶部的带隙小，致使表面对部分频率的太阳能有屏蔽作用。
步骤S140：开启所述微波功率源，使得所述微波等离子体产生室的惰性气体电离并产生微波等离子体，偏转线圈产生的磁场将微波等离子体从微波等离子体产生室引出至真空室，微波等离子体并对真空室内的所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子。
本申请通过微波等离子体对所述CIGS薄膜进行表面处理具有以下作用：1)微波等离子体在所述CIGS薄膜表面产生反溅射作用，可以清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子，方程式如下：Se+2e -＝Se2 -；3)由于微波等离子体作用在CIGS太阳能电池的表面，使得CIGS太阳能电池表面升温。
步骤S150：在表面改性的所述CIGS薄膜上制备所述i-ZnO和AZO窗口层。
步骤S160：在所述i-ZnO和AZO窗口层上沉积Ni/Al/Ni 栅电极。
在其中一些实施例中，还包括下述步骤：开启所述微波等离子体产生室与所述样品架之间的高压电源，在所述微波等离子体产生室与所述样品架之间加载高压，所述高压电源可高压加强所述微波等离子体的束流强度。
本申请提供的CIGS太阳能电池表面改性方法，采用微波等离子体对所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子，不仅可以去除表面的Cu-Se相，还可以减弱CIGS薄膜中Ga的不均匀状况，避免薄膜出现对太阳能的屏蔽作用，从而达到材料表面改性的目的，以获得了更高光电转换效率。此外，上述改性方法在密闭及非真空过程中的避免由于湿气造成的表面污染。
请参阅图2，为本申请一实施例提供的一种CIGS太阳能电池表面改性装置的结构示意图，包括：真空室110、设置于所述真空室110内及外侧的偏转线圈120、与所述真空室110连接的微波等离子体单元130，所述微波等离子体单元130包括微波功率源131、与所述微波功率源131连接的微波等离子体产生室132及围绕所述微波等离子体产生室132设置的磁场线圈133，所述微波等离子体产生室132与所述真空室110连接，所述真空室内还设置有CIGS薄膜。
在本实施例中，偏转线圈120为一根，围绕在真空室内侧和外侧；或者真空室内侧及真空室外侧均设置了偏转线圈。
本申请上述实施例提供的CIGS太阳能电池表面改性装置，其工作方式如下：
开启所述微波功率源131，使得所述微波等离子体产生室132的惰性气体电离并产生微波等离子体，所述偏转线圈120产生的磁场将所述微波等离子体从所述微波等离子体产生室132引出至所述真空室110，所述微波等离子体对所述真空室110内的所述CIGS薄膜100进行表面改性处理，微波等离子体在薄膜表面产生反溅射作用，可以清除CIGS薄膜表面的CuSe；游离态的Se吸收微波等离子体中的电子，转变成Se离子，且由于微波等离子体作用在CIGS薄膜的表面，使得CIGS薄膜升温。
在其中一些实施例中，所述真空室110的底部还设置有样品架140，所述CIGS薄膜100固定于所述样品架上。
在其中一些实施例中，所述磁场线圈133的磁场可调节，通过调节所述磁场线圈133产生的磁场与所述微波等离子体的微波频率相匹配。
在其中一些实施例中，所述微波等离子体产生室132与所述样品架140之间还加载有高压电源（图未示），所述高压电源可高压加强所述微波等离子体的束流强度。
在其中一些实施例中，所述磁场线圈133产生的磁场强度B与所述微波等离子体的微波频率f，满足关系2πf＝eB/m。
在其中一些实施例中，加载在所述微波等离子体产生室与所述样品架之间的高压电源电压在200V～1000V之间，所述微波等离子体的微波功率为45W，气体流量为5sccm，工作压强为2×10 -3p。
在其中一些实施例中，所述真空室110还连接有机械泵150，所述机械泵110可对所述真空室抽真空处理。
本申请提供的CIGS太阳能电池表面改性装置，采用微波等离子体对所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子，不仅可以去除表面的Cu-Se相，还可以减弱CIGS薄膜中Ga的不均匀状况，避免薄膜出现对太阳能的屏蔽作用，从而达到材料表面改性的目的，以获得了更高光电转换效率。此外，上述改性装置在密闭及非真空过程中的避免由于湿气造成的表面污染。
请参阅图3，本申请上述实施例提供的CIGS太阳能电池，包括依次层叠设置的钠钙玻璃衬底11、Mo背电极12、CIGS薄膜13、CdS缓冲层14、i-ZnO和AZO窗口层15及Ni-Al-Ni栅电极16。
在其中一些实施例中，所述Mo背电极120包括双层Mo薄膜，所述双层Mo薄膜包括一层疏松层及一层致密层，所述双层Mo薄膜的厚度为500-1000nm。
在其中一些实施例中，所述CIGS薄膜13包括88at.% 的GGI(Ga/([Ga]+[In])和35at.%的CIG(Cu/([Ga]+[In]))，所述CIGS薄膜13的厚度为1.8-3μm。
在其中一些实施例中，所述CdS缓冲层为n型CdS缓冲层，厚度为30-80nm。
在其中一些实施例中，所述i-ZnO和AZO窗口层中i-ZnO厚度为50-100nm，ZnO:Al厚度为100-300nm。
在其中一些实施例中，所述Ni-Al-Ni栅电极包括第一层Ni电极、蒸镀于所述第一层Ni电极上的Al电极及覆盖于所述Al电极上的第二层Ni电极，所述第一层Ni电极厚度为50-1000Å，所述Al电极厚度为5-10μm ，所述第二层Ni电极厚度为50-1000Å。
本申请上述实施例提供的CIGS太阳能电池，通过电离惰性气体产生等离子体，并作用到铜铟镓硒所述CIGS薄膜的表面，对所述CIGS薄膜进行等离子体退火和反溅射，不仅可以去除表面的Cu-Se相，还可以对薄膜进行进一步的退火，减弱Ga的不均匀状况，从而达到材料表面改性的目的。
以下结合具体实施例对本申请上述技术方案进行详细说明。
实施例1
1)用清洗机清洗衬底表面，共清洗4次，每次1h20min，在每次清洗间将衬底方向调换，除去表面的污染物与灰尘。清洗后用去离子水对衬底进行液封，避免污染；
2)利用直流射频磁控溅射在衬底上沉积Mo金属薄膜作为杂质元素阻挡层及背电极，并且实现Mo层与衬底较好的接触；
3)利用分子束外延三步共蒸发法在Mo薄膜上制备CIGS薄膜。除三步共蒸发法常规流程之外，在第一步开始同时以及第三步结束后，可利用碱金属氟化物NaF、KF进行处理，以减小禁带宽度减少晶界面与晶体内部缺陷，提高光电转化效率。
4)开启磁场线圈，调节电流使磁场线圈产生的磁场与微波的频率相匹配，为微波等离子体产生提供磁场基础；
5)向微波等离子体产生室送入H 2S，气体流量为5sccm，开启偏转线圈的电源，电源功率为45W，工作压强为2*10 -3Pa，偏转线圈产生的磁场将微波等离子体从产生室引出至样品架，对CIGS薄膜进行处理，时间为30min；
6)开启高压电源，在微波等离子体产生室与样品架之间加载高压加强等离子体束流强度；
7) 在完成表面改性处理后，在CIGS薄膜的表面制备CdS作为缓冲层以及P-N结形成层。以CdSO 4为镉源，硫脲为硫前驱体，NH 3•H 20为缓冲液，用水浴法在CIGS薄膜表面制备CdS薄膜，反应结束后以160℃进行退火。
8）利用磁控溅射法在表面制备本征氧化锌I-ZnO和掺铝掺杂氧化锌AZO薄膜，I-ZnO所用反应气体为Ar和O 2，Ar流量为200sccm，O 2流量为2sccm，起始溅射功率为120W，后续增加至220W。AZO所用反应气体为Ar和H 2，Ar流量为200sccm，H 2流量为2sccm，需在160℃保温15min，溅射功率为750W。
9）利用电子束蒸发法制备栅极。所用靶材为Ni和Al，其中Ni层厚度为1500Å，Al厚度为100000Å，得到栅极，完成CIGS太阳能电池制备过程。
可以理解，以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上仅为本申请的较佳实施例而已，仅具体描述了本申请的技术原理，这些描述只是为了解释本申请的原理，不能以任何方式解释为对本申请保护范围的限制。基于此处解释，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进，及本领域的技术人员不需要付出创造性的劳动即可联想到本申请的其他具体实施方式，均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种CIGS太阳能电池表面改性方法，其特征在于，包括下述步骤：
    在所述钠钙玻璃衬底上沉积所述Mo背电极；
    在所述Mo背电极上沉积所述CIGS吸收层；
    在所述CIGS吸收层上制备所述CIGS薄膜，包括：第一步，在360-390℃衬底温度下，在所述CIGS吸收层表面蒸发85-90%左右的In和Ga，形成(In,Ga) 2Se 3预制层；第二步，打开Cu源的挡板，只蒸发Cu，形成CIGS结晶；第三步，保持衬底温度与第二步相同，蒸发剩下的10%的In和Ga，保持蒸发的时间在15-20分钟，使其与第二步中过量的Cu反应，最终生成略贫Cu的CIGS薄膜；
    开启所述微波功率源，使得所述微波等离子体产生室的惰性气体电离并产生微波等离子体，偏转线圈产生的磁场将微波等离子体从微波等离子体产生室引出至真空室，微波等离子体并对真空室内的所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；2)游离态的Se吸收微波等离子体中的电子，转变成Se离子；
    在表面改性的所述CIGS薄膜上制备所述i-ZnO和AZO窗口层；
    在所述i-ZnO和AZO窗口层上沉积Ni/Al/Ni 栅电极。
  2. 如权利要求1所述的CIGS太阳能电池表面改性方法，其特征在于，还包括下述步骤：开启所述微波等离子体产生室与所述样品架之间的高压电源，在所述微波等离子体产生室与所述样品架之间加载高压。
  3. 如权利要求1所述的CIGS太阳能电池表面改性方法，其特征在于，在所述第一步中，在360-390℃衬底温度下，在所述CIGS吸收层表面还可以蒸发有NaF、KF或者在完成第三步后，于300℃温度下，再蒸镀一层NaF或KF层。
  4. 一种如权利要求1所述的CIGS太阳能电池表面改性方法的改性装置，其特征在于，包括真空室、设置于所述真空室内及外侧的偏转线圈、与所述真空室连接的微波等离子体单元，所述微波等离子体单元包括微波功率源、与所述微波功率源连接的微波等离子体产生室及围绕所述微波等离子体产生室设置的磁场线圈，所述微波等离子体产生室与所述真空室连接，所述真空室内还设置有所述CIGS薄膜；
    开启所述微波功率源，使得所述微波等离子体产生室的惰性气体电离并产生微波等离子体，所述偏转线圈产生的磁场将所述微波等离子体从所述微波等离子体产生室引出至所述真空室，所述微波等离子体对所述CIGS薄膜进行表面改性处理，所述微波等离子体在所述CIGS薄膜表面清除所述CIGS薄膜表面的CuSe；游离态的Se吸收微波等离子体中的电子，转变成Se离子。
  5. 如权利要求4所述的CIGS太阳能电池表面改性装置，其特征在于，所述磁场线圈的磁场可调节，通过调节所述磁场线圈产生的磁场与所述微波等离子体的微波频率相匹配。
  6. 如权利要求5所述的CIGS太阳能电池表面改性装置，其特征在于，所述微波等离子体产生室与所述样品架之间还加载有高压电源，所述高压电源可高压加强所述微波等离子体的束流强度。
  7. 如权利要求6所述的CIGS太阳能电池表面改性装置，其特征在于，所述磁场线圈产生的磁场强度B与所述微波等离子体的微波频率f，满足关系2πf＝eB/m。
  8. 如权利要求7所述的CIGS太阳能电池表面改性装置，其特征在于，加载在所述微波等离子体产生室与所述样品架之间的高压电源电压在200V～1000V之间，所述微波等离子体的微波功率为45W，气体流量为5sccm，工作压强为2×10 -3p。
  9. 如权利要求3所述的CIGS太阳能电池表面改性装置，其特征在于，所述真空室还连接有机械泵，所述机械泵可对所述真空室抽真空处理。
  10. 一种CIGS太阳能电池，其特征在于，由权利要求1所述的CIGS太阳能电池表面改性方法得到，包括依次层叠设置的钠钙玻璃衬底、Mo背电极、CIGS薄膜、CdS缓冲层、i-ZnO和AZO窗口层及Ni-Al-Ni栅电极，所述CIGS薄膜的表面经微波等离子体改性处理。
PCT/CN2022/138194 2022-09-22 2022-12-09 Cigs太阳能电池表面改性方法、装置及cigs太阳能电池 Ceased WO2024060423A1 (zh)

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