WO2011130888A1 - System and method for manufacturing semiconductor thin film solar cell - Google Patents

System and method for manufacturing semiconductor thin film solar cell Download PDF

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Publication number
WO2011130888A1
WO2011130888A1 PCT/CN2010/001286 CN2010001286W WO2011130888A1 WO 2011130888 A1 WO2011130888 A1 WO 2011130888A1 CN 2010001286 W CN2010001286 W CN 2010001286W WO 2011130888 A1 WO2011130888 A1 WO 2011130888A1
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Prior art keywords
temperature
production line
channel type
type multi
heating device
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PCT/CN2010/001286
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French (fr)
Chinese (zh)
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林朝晖
李晓常
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福建钧石能源有限公司
北京精诚铂阳光电设备有限公司
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Publication of WO2011130888A1 publication Critical patent/WO2011130888A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67098—Apparatus for thermal treatment
    • H01L21/67109—Apparatus for thermal treatment mainly by convection
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
    • H01L21/67161—Apparatus for manufacturing or treating in a plurality of work-stations characterized by the layout of the process chambers
    • H01L21/67173—Apparatus for manufacturing or treating in a plurality of work-stations characterized by the layout of the process chambers in-line arrangement
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/673—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere using specially adapted carriers or holders; Fixing the workpieces on such carriers or holders
    • H01L21/6735—Closed carriers
    • H01L21/67389—Closed carriers characterised by atmosphere control
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/677—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations
    • H01L21/67739—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for conveying, e.g. between different workstations into and out of processing chamber
    • H01L21/6776—Continuous loading and unloading into and out of a processing chamber, e.g. transporting belts within processing chambers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the technical field of photovoltaic solar cell manufacturing, and in particular to a semiconductor thin film solar cell, in particular to a manufacturing system and a manufacturing method of a copper indium gallium selenide thin film solar cell. Background technique
  • the copper indium gallium selenide thin film solar cell has the characteristics of low production cost, low pollution, no degradation, stable performance, strong radiation resistance, good low light performance, etc.
  • the photoelectric conversion efficiency ranks first among various thin film solar cells, close to the current market owner.
  • the battery has a soft, uniform black appearance, which is ideal for places with high requirements for appearance, such as glass curtain walls for large buildings, and has a large market in modern high-rise buildings, whether it is on the ground or not. It still has broad market prospects in the application of space microsatellite power supplies.
  • the manufacturing method of the copper indium gallium selenide compound absorption film can be roughly divided into two types, a co-evaporation method and a pre-formed film + selenization method.
  • the co-evaporation method is a direct method to prepare a CIGS crystal film of high quality and having a gradient of chalcopyrite structure.
  • the co-evaporation method essentially involves the formation of In (Ga) 2 Se 3 , copper-rich CIGS and copper-free CIGS, and finally reaches a copper atomic percentage of 23.5%, indium.
  • the CIGS film has an atomic percentage of 19.5%, a gallium atom percentage of 7%, and a selenium atom percentage of 50%.
  • the co-evaporation method not only requires a precise evaporation rate ratio that changes with time, but also requires the glass substrate to be heated to 42 (T600 ° C, which is demanding for temperature control, because whenever the copper source temperature fluctuates by 20 ° C) , will lead to 50% copper evaporation rate changes, it is difficult to form large-scale low-cost mass production.
  • the preform film + selenization method is to prepare a precursor film containing copper, indium and gallium while the glass substrate is kept at room temperature, and then heating the glass substrate to 40 CT 600 ° C.
  • the selenization reaction forms a CIGS polycrystalline film.
  • the precursor film can be continuously prepared by thermal evaporation, or magnetron sputtering, or nano ink coating.
  • the selenization reaction is usually carried out in a vacuum or an inert atmosphere chamber using hydrogen selenide or selenium vapor as a reaction gas at 40 ° C (T600 ° C.
  • the multi-piece preform substrate can be subjected to intermittent one-time selenization or a plurality of preforms separately placed in a stacked selenization chamber. Regardless of the selenization reaction method, the previous selenization process undergoes a process of heating and cooling in the vacuum chamber.
  • the temperature in the furnace body is controlled, and the temperature change of the furnace body can be expressed as A process curve that experiences heating, constant temperature, and cooling, such as 150 ° C (5 minutes constant), 320 ° C (5 minutes constant), 420 ° C (15 minutes constant), and 550 ° C (15 minutes constant).
  • the temperature rise and fall mode is simple and easy to implement, the temperature rise and temperature drop process will have a large temperature shock and fluctuation, the temperature stability and stability during the constant temperature process are poor, and the temperature rise and fall takes a long time, and cannot be achieved. Rapid continuous production, each additional temperature/cooling cycle also brings additional energy loss.
  • a copper indium gallium selenide polycrystalline thin film solar absorbing layer is produced.
  • the present invention provides a manufacturing system for a semiconductor thin film solar cell, comprising:
  • a channel type multi-temperature zone heating device having a plurality of fixed temperature zones
  • a production line consisting of a plurality of thermochemical reaction vessels capable of adjusting an atmosphere; and a rotating mechanism and a control member, the control member controlling the rotating mechanism to drive the thermochemical reaction vessels on the production line sequentially through the channel type multi-temperature zone A plurality of fixed temperature zones of the heating device.
  • the production line is fixed, and the control component controls the rotating mechanism to drive the channel type multi-temperature zone heating device to move along the production line.
  • the channel type multi-zone heating device is fixed, and the control component controls the rotating mechanism to drive the production line to move.
  • the production line is circular, and the channel type multi-temperature zone heating device has a circular arc shape.
  • the production line is in the form of a combination of a straight line and a circular shape similar to the shape of the track field, or a form in which any arc is connected to the first position of the straight line.
  • the channel type multi-zone heating device is linear or arc-shaped.
  • the atmosphere includes hydrogen sulfide, hydrogen sulfide, organic selenide, organic sulfide, high temperature selenium vapor, high temperature sulfur vapor, and a mixed gas of two or more of inert gases.
  • the present invention provides a method of fabricating another semiconductor thin film solar cell, comprising:
  • the substrate carrying the compound semiconductor precursor is placed in an atmosphere-adjustable reaction vessel;
  • a production line consisting of a plurality of said reaction vessels sequentially passes through a channel type multi-temperature zone heating device having a plurality of fixed temperature zones;
  • the substrate in the reaction vessel undergoes a temperature rise and fall process to complete the thermochemical reaction required to fabricate the semiconductor thin film solar cell.
  • the production line is fixed, and the control unit controls the rotating mechanism to drive the channel type multi-temperature zone heating device to move along the production line.
  • the channel type multi-temperature zone heating device is fixed, and the control component controls the rotation mechanism to drive the production line to move.
  • the production line is circular, and the channel type multi-temperature zone heating device has a circular arc shape.
  • the production line is in the form of a combination of a straight line and a circle similar to the shape of the track field, or any arc connected to the first position of the straight line, and the channel type multi-temperature zone heating device is linear or arc-shaped.
  • the plurality of fixed temperature zones includes a temperature rising zone, an alloying zone, a selenization zone, a sulfurization zone, and an annealing zone.
  • the reaction vessel is a temperature resistant and corrosion resistant quartz glass or metal case.
  • the physical coating method comprises a vacuum hot coating method, a magnetron sputtering method, an electrochemical coating method or a wet coating method.
  • the wet coating method comprises a printing method such as spin coating, spray coating, silk screen printing, dripping coating, dip coating or the like.
  • the present invention has the following advantages:
  • the system and method for fabricating a semiconductor thin film solar cell of the present invention provides a new and superior process for the thermochemical reaction with a temperature rise and fall process.
  • the manufacturing system of the semiconductor thin film solar cell of the present invention adopts a channel type multi-temperature zone heating device, and the device has a plurality of fixed temperature zones whose temperatures are set according to process requirements, and the temperature in each temperature zone is constant.
  • the reaction vessel is rotated relative to the channel type multi-temperature zone heating device by a rotating mechanism, and the reaction vessel sequentially enters the channel type multi-temperature zone heating device according to a preset speed, sequentially passes through each temperature zone with constant temperature, and then exits the channel type.
  • thermochemical reaction in each reaction vessel
  • the substrate, the substrate or the glass substrate which is required to undergo the thermochemical reaction can continuously and sequentially pass through each of the constant temperature zones, and the corresponding process with the least temperature fluctuation is performed in each constant temperature zone. After each constant temperature zone, the entire thermochemical reaction process corresponding to the temperature rise and fall process conditions is completed.
  • the manufacturing system and method for the semiconductor thin film solar cell of the present invention avoids the temperature fluctuation and impact of the conventional temperature rise and fall process during the temperature change operation in the same reaction chamber, so that the substrate, the substrate or the glass substrate in each reaction container It is able to smoothly obtain the rise/fall temperature and optimize the thermochemical reaction conditions, which is especially suitable for the selenization thermochemical reaction in the manufacturing process of CIGS thin film solar cells. Moreover, since there is no temperature rise and fall process, the time required for the temperature rise and fall is greatly saved, and the production efficiency is improved.
  • the rotating mechanism of the manufacturing system of the semiconductor thin film solar cell of the present invention can place a plurality of reaction vessels, and each of the reaction vessels can be placed with a plurality of substrates such as glass substrates, and the loading operation before entering the channel type multi-temperature zone heating device And the unloading operation after exiting the multi-zone heating device enables the invention to manufacture CIGS polycrystalline film with high yield and continuous uninterrupted production, which greatly improves the production capacity and meets the needs of industrial production.
  • FIG. 1 is a temperature profile illustrating a temperature change process generally performed in the same reaction chamber
  • FIG. 2 is a semiconductor thin film solar cell manufacturing system according to a first embodiment of the present invention. Show Intention
  • Figure 3 is a temperature chart illustrating the temperature change process of the present invention
  • Fig. 4 is a view showing a semiconductor thin film solar cell manufacturing system according to a second embodiment of the present invention.
  • FIG. 1 is a graph showing the temperature profile of a temperature swing process typically performed in the same reaction chamber. Specifically, FIG. 1 is a temperature profile for performing a thermochemical reaction of copper indium gallium selenide. As shown in FIG. 1, a copper indium (1:1) metal preform is deposited on a molybdenum-plated glass substrate. The glass substrate was then heated to 150 ° C and held for 5 minutes to remove adsorbed water or oxygen.
  • the substrate was then heated in a reaction vessel to 320 ° C and held for 5 minutes to fully alloy the copper-indium metal. After the reaction container is in communication The temperature was raised to 420 ° C in the case of 3 ⁇ 4 Se and held for 20 minutes to promote selenization of the copper-indium alloy to form an initial copper indium selenide semiconductor film.
  • the copper indium selenide film substrate formed by the thermal selenization reaction is formed and can be taken out from the reaction vessel for use in the next process.
  • the general way to achieve the rising/lowering thermochemical reaction shown in Figure 1 is to place the reaction vessel containing the substrate in a reaction chamber, and the temperature of the reaction chamber is raised or lowered by electric power control by means of a heating element, thereby making the reaction vessel
  • the inner substrate undergoes a temperature change process.
  • electrical power-controlled heating elements become temperature-dependent over time, large temperature shocks and fluctuations (25 °C, as shown by the curves at ⁇ , ⁇ 2, ⁇ 3, and ⁇ 4) are inevitably generated. This large temperature oscillation often results in uneven quality in different regions of the final solar cell, as well as mass differences between the sheets, even the deformation of the glass substrate. All of this will result in low yields and high yields.
  • the manufacturing system and method for the semiconductor thin film solar cell of the present invention is a thermochemical reaction having a temperature rise and fall process, and in particular, the selenization thermochemical reaction of interest herein provides a new and superior process.
  • 2 is a schematic view showing a semiconductor thin film solar cell manufacturing system according to a first embodiment of the present invention. As shown in FIG.
  • the semiconductor thin film solar cell manufacturing system of the present invention comprises a channel type multi-temperature zone heating device 70 having a large aspect ratio; a plurality of thermochemical reaction vessels 71 for accommodating a solar film glass substrate;
  • the mechanism 72 drives the reaction vessel 71 to run on the rail by the connecting rod 78;
  • the gas supply station 73 for controlling the atmosphere (such as vacuum, inert gas or reaction gas); for controlling the channel type multi-temperature zone heating device 70 and thermochemistry Reaction
  • a control station 74 for the relative movement speed between the containers 71; a loading area 75 for manually or automatically loading the inside of the reaction container 71; and a discharge area 76 for taking out the substrate from the reaction container 71.
  • the semiconductor thin film solar cell manufacturing system of the present invention may further include an exhaust gas treatment system and a corresponding safety sensor detector.
  • a plurality of temperature zones of a specific temperature are disposed in the channel type multi-temperature zone heating device 70, and the reaction vessels 71 sequentially pass through the respective temperature zones in the order of the arrow direction. . That is, the helium zone, the T2 zone, the T3 zone, the T4 zone and the T5 zone, and the temperature in each temperature zone is constant.
  • ⁇ zone dehumidification deoxidation zone
  • the temperature is set to 150 ° C, in this temperature zone, the glass substrate is heated to 150 ° C in the reaction vessel under vacuum
  • T2 zone alloying zone, temperature Set to 320 ° C, in this temperature zone, the preformed metal on the glass substrate is alloyed
  • T3 zone Selenization thermochemical reaction zone, temperature set to 420 °C, prefabricated in this zone The selenization reaction is carried out into a copper indium selenide semiconductor film
  • T4 region a crystalline perfect region, the temperature is set to 550 ° C, in this temperature region, the crystal grains of the semiconductor thin film form large grains lm)
  • T5 region annealing and cooling
  • the temperature is set to about 80 ° C. In this temperature zone, the glass substrate is cooled and annealed to prepare a sheet.
  • the channel type multi-zone heating device 70 can accommodate a plurality of thermochemical reaction vessels 71 spaced apart from each other, and a suitable number is 3000, generally 5 to 500, apparently covered by the channel type multi-zone heating device 70.
  • the number of reaction vessels 71 the length of which can vary accordingly. Therefore, regardless of the length of the channel type multi-zone heating device 70, it is within the scope of the present invention.
  • a suitable length is 5 to 500 meters. The longer the length, the more reaction vessels are accommodated or covered, and the larger the yield per unit time.
  • Channel type multi-temperature zone heating device 70 fixed temperature zone The quantity is set according to the actual process requirements, and the length of each temperature zone is set according to the reaction time requirement.
  • the residence time of the glass substrate in the crotch region, the T2 region, the T3 region, the T4 region, and the T5 region was 5 minutes, 5 minutes, 20 minutes, 15 minutes, and 15 minutes, respectively.
  • the lengths of the crotch region, the T2 region, the T3 region, the T4 region and the T5 region depend on the residence time of the substrate, and the speed of rotation of the rotating mechanism 72 is controlled by the control station 74 to cause each temperature in the passage of the reaction vessel 71 at an appropriate speed. Run in the zone to meet process requirements.
  • Figure 3 is a graph showing the temperature profile of the temperature change process of the present invention. As can be seen from FIG.
  • the temperature change process of the present invention does not require temperature rise and fall, but smoothly passes through various different temperature zones, and the temperature of each temperature zone is substantially constant, and there is substantially no temperature fluctuation.
  • the reaction vessel 71 carrying the preform slowly passes through the respective temperature zones at a certain speed, the temperature rise and fall process is realized, and the temperature fluctuation of the glass substrate in the reaction vessel 71 during the temperature rise and fall process tends to be minimum (less than 3 ⁇ ) 5 °C).
  • the temperature rise and fall time of the conventional heating is omitted, and the production efficiency is improved.
  • the channel type multi-temperature zone heating device 70 of the present invention includes a heating element, a holding furnace body, a temperature control member, a moving rail, and the like.
  • the heating element can be heated by combustion ignition or more convenient electric heating. Other heating methods such as induction heating, microwave heating, etc. can also be used. Since the chemical reaction is usually at 20 (T600 ° C, the channel type multi-zone heating device 70 needs to be well insulated, the suitable material can generally be any material with both mechanical strength and thermal insulation, such as ceramics, glass, brick, Multi-layer graphite or ceramic fiber cotton, etc.
  • Temperature-control components are generally composed of temperature detection, display, setting, and control, etc. Those skilled in the art can establish and implement such temperature-control components.
  • each of the above temperature zones is to prepare a copper indium selenide semiconductor film.
  • each specific temperature can be changed accordingly, and is within the scope of the present invention.
  • One way to create relative motion between the channel type multi-zone heating device 70 and the selenization reaction vessel 71 is to mount a plurality of reaction vessels 71 on a heat resistant material shaft or ball, such as alumina, or a ceramic shaft (or ceramic ball). Rolling on the track moves the reaction vessel 71 through the channel type multi-zone heating device 70.
  • Another way to generate relative motion is to move the channel-type multi-temperature zone heating device to achieve a cooling process while the stationary selenization reaction vessel is stationary.
  • Fig. 4 is a view showing a semiconductor thin film solar cell manufacturing system according to a second embodiment of the present invention.
  • Fig. 4 is a view showing a semiconductor thin film solar cell manufacturing system in which a channel type multi-zone heating device is moved according to a preferred embodiment of the present invention.
  • the control unit controls the rotating mechanism to drive the channel type multi-temperature zone heating device 80 to slowly move on the track 82 at a certain speed.
  • the heating reaction container 81 sequentially passes through the respective constant temperature.
  • the gas source zone 87 provides various atmospheres for the reaction vessel 81, the vacuum system 86 provides a vacuum environment, the operator 85 performs the loading and unloading operations, and the exhaust gas treatment system 84 treats the exhaust gases.
  • the selenization reaction vessel 81 is usually connected to a pipe such as a vacuum, an inert gas, a reaction gas, and an exhaust gas outlet, it is more preferable to move the channel type multi-temperature zone heating device 80. Therefore, the guide rails 82 are mounted under the channel type multi-zone heating device 80 to operate as a railed electric train or diesel locomotive as a preferred mode of motion of the present invention.
  • the selenization reaction vessel in the furnace body can be heated and lowered. Since the temperature in each temperature zone of the furnace is constant, the temperature fluctuation experienced by each reaction vessel is minimal.
  • Temperature fluctuation is the difference between the set temperature and the actual temperature.
  • a heating element has to adjust different temperatures over time, it is inevitable to generate a temperature shock or oscillation, resulting in a difference between the set value and the actual value.
  • the heating element at this time maintains a steady state of a given heat, minimizing the temperature difference between the set value and the actual value, and is most advantageous for achieving high yield production.
  • the present invention does not exclude linear motion between the channel type multi-temperature zone heating device and the selenization reaction device, that is, a linear motion channel type multi-temperature zone heating device.
  • the most preferred way is that the reaction vessels are connected in the first place and arranged in a circular production line, and the channel-type multi-temperature zone heating device has a circular arc shape, as shown in FIG. It can also be a combination of a straight line in the shape of a track field and a circle, or a production line in which any arc is connected to the first position of the line.
  • the biggest benefit of the end-to-end connection is that the reaction vessel and the channel-type multi-zone heating unit can be reciprocated and continuously operated continuously, without interruption.
  • the length of the end-to-end production line can be 2CT500m, and the suitable total length is 3CT300m.
  • the end-to-end production line is provided with a loading area for loading the preformed glass substrate and performing necessary leak detection, safety inspection and thermochemical preparation; unloading area, for substrate Cooling and unpacking;
  • the area where the channel type multi-temperature zone heating device is located may be called a thermochemical reaction zone or a selenization zone for effective thermochemical reaction or selenization reaction.
  • the reaction vessel includes a temperature and chemical resistant chamber and a door for loading and unloading the glass substrate, and an inlet and outlet line for evacuating and controlling the atmosphere.
  • Suitable cavity and door materials can be made of temperature-resistant and corrosion-resistant stainless steel or quartz glass, corundum and the like. Considering mechanical strength, cost and The processing is simple, preferably stainless steel.
  • the reaction vessel lining may be made of quartz glass, ceramic or graphite as an inner liner.
  • a metal layer such as molybdenum, titanium, chromium or other alloy, a physical coating method such as magnetron sputtering or vacuum evaporation may be employed to obtain a back electrode having both conductive and reflective functions.
  • the substrate may also use a metal flexible substrate such as stainless steel or aluminum foil or the like.
  • a film of an electrically insulating material such as silicon dioxide, is first grown on the surface of the metal flexible substrate, and then a reflective back electrode is formed by physical plating.
  • a polymer film can also be used as the substrate, and in view of heat resistance requirements, currently suitable polymers are polyimide, polyetheretheramine, polysulfonymine, and the like.
  • the reflective conductive electrode metal may be plated on one side of the polymer or, more preferably, on both sides of the polymer to increase heat resistance and avoid deformation of the substrate.
  • the semiconductor referred to in the present invention may also be a III-V semiconductor such as GaAs, InP or the like.
  • their precursors that is, metal or compound precursor films containing all or most of the elements, may be prepared, and then these precursors are heated while introducing a reaction gas such as H 2 S, H 2 . Se, 3 ⁇ 4P, 3 ⁇ 4AS, etc. form a compound semiconductor.

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Abstract

A system and a method for manufacturing semiconductor thin film solar cell are provided. The system comprises: channel heating means with several temperature zones (70); a plurality of thermo-chemical reaction containers (71) for containing thin film substrates; a rotation mechanism (72) driving the thermo-chemical reaction containers (71); a gas supplying station (73) for controlling the ambient; a control station (74) for controlling the relative movement between the channel heating means with several temperature zones (70) and the thermo-chemical reaction containers (71). The temperature of the substrates in the thermo-chemical reaction containers (71) varies continuously and stably following the relative movement between the production lines and the channel heating means with several temperature zones (70), thus the thermo-chemical reaction which is required in the production of semiconductor thin film solar cell is accomplished.

Description

半导体薄膜太阳能电池的制造系统和方法 技术领域  Semiconductor thin film solar cell manufacturing system and method
本发明涉及光伏太阳能电池制造技术领域， 具体涉及一种半导体薄 膜太阳能电池， 特别是铜铟镓硒薄膜太阳能电池的制造系统和制造方法。 背景技术  The invention relates to the technical field of photovoltaic solar cell manufacturing, and in particular to a semiconductor thin film solar cell, in particular to a manufacturing system and a manufacturing method of a copper indium gallium selenide thin film solar cell. Background technique
随着能源消耗的不断增加， 作为能源的主要来源， 石油和煤炭的大 量使用所导致的二氧化碳排放严重地污染生态环境， 而且石油和煤炭资 源也面临枯竭的境地， 因此， 寻求低碳排放而又取之不尽的可再生能源 变得越来越紧迫， 基于光伏效应的太阳能电池正是这样一种可再生新能 源。 当前， 人们对太阳能的开发和利用日趋重视， 市场对更大面积、 更 轻更薄且生产成本更低的新型太阳能电池的需求日益增加。 在这些新型 太阳能电池中， 近年来开发出来的基于硅材料的合金薄膜太阳能电池， 例如非晶硅和碲化镉薄膜太阳能电池， 以其用硅量少、 低成本、 低能耗 和高量产等特性， 已成为太阳能电池发展的新趋势和新热点。 虽然薄膜 太阳能电池具有上述优势， 但是非晶硅薄膜太阳能电池有光电转换效率 低和稳定性欠佳等缺点； 而碲化镉薄膜太阳能电池则有环保要求对镉金 属的使用限制。  As energy consumption continues to increase, as a major source of energy, carbon dioxide emissions caused by the heavy use of oil and coal seriously pollute the ecological environment, and oil and coal resources are also facing depletion, so seek low carbon emissions. Inexhaustible renewable energy is becoming more and more urgent, and solar cells based on photovoltaic effect are such a renewable new energy source. At present, people are paying more and more attention to the development and utilization of solar energy, and the demand for new solar cells with larger area, lighter and thinner, and lower production cost is increasing. Among these new types of solar cells, silicon-based alloy thin film solar cells, such as amorphous silicon and cadmium telluride thin film solar cells, which have been developed in recent years, use less silicon, low cost, low energy consumption, and high mass production. Characteristics have become a new trend and new hotspot in the development of solar cells. Although thin film solar cells have the above advantages, amorphous silicon thin film solar cells have disadvantages such as low photoelectric conversion efficiency and poor stability; while cadmium telluride thin film solar cells have environmental protection requirements for the use of cadmium metals.
近年来， 学术界又研制出了基于半导体铜铟镓硒等化合物 In recent years, the academic community has developed compounds based on semiconductor copper, indium gallium selenide and the like.
(CuInGaSe2, CIGS) 的薄膜太阳能电池。 铜铟镓硒薄膜太阳能电池具有 生产成本低、 污染小、 不衰退、 性能稳定、 抗辐射能力强、 弱光性能好 等特点， 光电转换效率居各种薄膜太阳能电池之首， 接近于目前市场主 流产品晶体硅太阳能电池的转换效率， 而成本则是晶体硅电池的三分之 一， 被国际上称为 "下一时代非常有前途的新型廉价薄膜太阳能电池" 。 此外， 该电池具有柔和、 均匀的黑色外观， 是对外观有较高要求场所的 理想选择， 如大型建筑物的玻璃幕墙等， 在现代化高层建筑等领域有很 大市场， 无论是在地面阳光发电还是在空间微小卫星动力电源的应用上 具有广阔的市场前景。 Thin film solar cells (CuInGaSe 2 , CIGS). The copper indium gallium selenide thin film solar cell has the characteristics of low production cost, low pollution, no degradation, stable performance, strong radiation resistance, good low light performance, etc. The photoelectric conversion efficiency ranks first among various thin film solar cells, close to the current market owner. The conversion efficiency of crystalline silicon solar cells, while the cost is one-third of that of crystalline silicon cells, is internationally called "a new era of low-cost thin-film solar cells of the next era." In addition, the battery has a soft, uniform black appearance, which is ideal for places with high requirements for appearance, such as glass curtain walls for large buildings, and has a large market in modern high-rise buildings, whether it is on the ground or not. It still has broad market prospects in the application of space microsatellite power supplies.
铜铟镓硒化合物吸收薄膜的制造方法大体可分为两种， 共蒸发法和 预制体薄膜 +硒化二歩法。共蒸发法是直接一歩的方法制备出高质量并有 能带梯度的黄铜矿结构的 CIGS晶体薄膜。然而， 为了获得高质量的 CIGS 薄膜，共蒸发一歩法实质上涉及了形成 In (Ga) 2Se3，富铜 CIGS及少铜 CIGS 三个阶段， 最终达到铜原子百分比为 23. 5%， 铟原子百分比为 19. 5%， 镓 原子百分比为 7%， 硒原子百分比为 50%的 CIGS薄膜。 显然， 共蒸发法不 仅要求随时间而变的精准的蒸发速度配比， 而且要求玻璃基板被加热到 42(T600°C， 对温度控制的要求苛刻， 因为每当铜源温度波动 20°C时， 会 导致 50%铜蒸发速度的变化， 难以形成大规模低成本量产。 The manufacturing method of the copper indium gallium selenide compound absorption film can be roughly divided into two types, a co-evaporation method and a pre-formed film + selenization method. The co-evaporation method is a direct method to prepare a CIGS crystal film of high quality and having a gradient of chalcopyrite structure. However, in order to obtain a high-quality CIGS film, the co-evaporation method essentially involves the formation of In (Ga) 2 Se 3 , copper-rich CIGS and copper-free CIGS, and finally reaches a copper atomic percentage of 23.5%, indium. The CIGS film has an atomic percentage of 19.5%, a gallium atom percentage of 7%, and a selenium atom percentage of 50%. Obviously, the co-evaporation method not only requires a precise evaporation rate ratio that changes with time, but also requires the glass substrate to be heated to 42 (T600 ° C, which is demanding for temperature control, because whenever the copper source temperature fluctuates by 20 ° C) , will lead to 50% copper evaporation rate changes, it is difficult to form large-scale low-cost mass production.
另一种方法， 预制体薄膜 +硒化二歩法是在玻璃基片保持在室温的情 况下制得含铜、 铟、 镓的前驱体薄膜， 然后把玻璃基片加热到 40CT600 °C下进行硒化反应形成 CIGS多晶薄膜。 该方法较共蒸发法更简便易于大 规模生产控制。 在该方法中， 前驱体薄膜可以采用热蒸发， 或磁控溅射， 或是纳米油墨涂覆等方法连续制备。 硒化反应通常是在真空或惰性气氛 室中， 采用硒化氢或硒蒸气作为反应气体， 于 40(T600°C下进行。 为了增 加产量， 多片预制体基片可进行间歇式一次硒化或把多片预制体分别置 于叠层式硒化腔体中进行。 无论采用何种硒化反应方式， 以往的硒化过 程在真空腔室中都要经历一个升温和降温的过程， 通过调节炉体内的电 加热功率来控制炉体内温度， 炉体温度变化可表现为一条经历升温、 恒 温和降温的工艺曲线， 如 150°C (恒温 5分钟）、 320°C (恒温 5分钟）、 420 °C (恒温 15分钟）和 550°C (恒温 15分钟）。 这种升降温方式虽然简 便易于实现， 但升温和降温过程会有很大的温度冲击和波动， 恒温过程 中的温度稳定性和平稳性较差， 而且升降温都需要很长时间， 无法做到 快速连续生产， 每一个升 /降温周期还会带来额外的能量损耗。 In another method, the preform film + selenization method is to prepare a precursor film containing copper, indium and gallium while the glass substrate is kept at room temperature, and then heating the glass substrate to 40 CT 600 ° C. The selenization reaction forms a CIGS polycrystalline film. This method is simpler than the co-evaporation method and is easy to control in large-scale production. In this method, the precursor film can be continuously prepared by thermal evaporation, or magnetron sputtering, or nano ink coating. The selenization reaction is usually carried out in a vacuum or an inert atmosphere chamber using hydrogen selenide or selenium vapor as a reaction gas at 40 ° C (T600 ° C. To increase the yield, the multi-piece preform substrate can be subjected to intermittent one-time selenization or a plurality of preforms separately placed in a stacked selenization chamber. Regardless of the selenization reaction method, the previous selenization process undergoes a process of heating and cooling in the vacuum chamber. By adjusting the electric heating power in the furnace body, the temperature in the furnace body is controlled, and the temperature change of the furnace body can be expressed as A process curve that experiences heating, constant temperature, and cooling, such as 150 ° C (5 minutes constant), 320 ° C (5 minutes constant), 420 ° C (15 minutes constant), and 550 ° C (15 minutes constant). Although the temperature rise and fall mode is simple and easy to implement, the temperature rise and temperature drop process will have a large temperature shock and fluctuation, the temperature stability and stability during the constant temperature process are poor, and the temperature rise and fall takes a long time, and cannot be achieved. Rapid continuous production, each additional temperature/cooling cycle also brings additional energy loss.
发明内容 Summary of the invention
因此， 本发明的目的在于提供一种半导体薄膜太阳能电池的制造系 统和方法， 能够在热化学反应生成化合物薄膜的过程中提供连续、 平稳 的变温反应条件， 特别适合于高量产、 连续、 平稳地制造铜铟镓硒多晶 薄膜太阳能吸收层。  Accordingly, it is an object of the present invention to provide a system and method for fabricating a semiconductor thin film solar cell capable of providing a continuous and stable temperature-changing reaction condition in a process of thermochemically reacting a compound film, which is particularly suitable for high-volume production, continuous, and smooth operation. A copper indium gallium selenide polycrystalline thin film solar absorbing layer is produced.
一方面， 本发明提供了一种半导体薄膜太阳能电池的制造系统， 包 括：  In one aspect, the present invention provides a manufacturing system for a semiconductor thin film solar cell, comprising:
具有复数个固定温区的通道式多温区加热装置；  a channel type multi-temperature zone heating device having a plurality of fixed temperature zones;
由复数个可调节气氛的热化学反应容器组成的生产线； 以及 旋转机构和控制部件， 所述控制部件控制所述旋转机构驱动所述生 产线上的热化学反应容器顺序通过所述通道式多温区加热装置的复数个 固定温区。 可选的， 所述生产线固定不动， 所述控制部件控制所述旋转机构驱 动所述通道式多温区加热装置沿着生产线移动。 a production line consisting of a plurality of thermochemical reaction vessels capable of adjusting an atmosphere; and a rotating mechanism and a control member, the control member controlling the rotating mechanism to drive the thermochemical reaction vessels on the production line sequentially through the channel type multi-temperature zone A plurality of fixed temperature zones of the heating device. Optionally, the production line is fixed, and the control component controls the rotating mechanism to drive the channel type multi-temperature zone heating device to move along the production line.
可选的， 所述通道式多温区加热装置固定不动， 所述控制部件控制 所述旋转机构驱动生产线移动。  Optionally, the channel type multi-zone heating device is fixed, and the control component controls the rotating mechanism to drive the production line to move.
可选的， 所述生产线为圆形， 所述通道式多温区加热装置为圆弧形。 可选的， 所述生产线为类似田径场形状的直线与圆形相结合的形式， 或任何圆弧与直线首位相连的形式。  Optionally, the production line is circular, and the channel type multi-temperature zone heating device has a circular arc shape. Optionally, the production line is in the form of a combination of a straight line and a circular shape similar to the shape of the track field, or a form in which any arc is connected to the first position of the straight line.
可选的， 所述通道式多温区加热装置为直线型或圆弧形。  Optionally, the channel type multi-zone heating device is linear or arc-shaped.
可选的， 所述气氛包括硒化氢、 硫化氢、 有机硒化物、 有机硫化物、 高温硒蒸气、 高温硫蒸气， 以及惰性气体中的两种或多种的混合气体。  Optionally, the atmosphere includes hydrogen sulfide, hydrogen sulfide, organic selenide, organic sulfide, high temperature selenium vapor, high temperature sulfur vapor, and a mixed gas of two or more of inert gases.
另一方面， 本发明提供了另一种半导体薄膜太阳能电池的制造方法， 包括：  In another aspect, the present invention provides a method of fabricating another semiconductor thin film solar cell, comprising:
在导电电极上通过物理镀膜法制备化合物半导体前驱体；  Preparing a compound semiconductor precursor by a physical plating method on the conductive electrode;
把载有所述化合物半导体前驱体的基片置于一气氛可调的反应容 器；  The substrate carrying the compound semiconductor precursor is placed in an atmosphere-adjustable reaction vessel;
由复数个所述反应容器组成的生产线依次经过具有复数个固定温区 的通道式多温区加热装置；  a production line consisting of a plurality of said reaction vessels sequentially passes through a channel type multi-temperature zone heating device having a plurality of fixed temperature zones;
随着所述生产线与所述通道式多温区加热装置的相对移动， 所述反 应容器内的基片经历升降温过程而完成制造半导体薄膜太阳能电池所需 的热化学反应。  With the relative movement of the production line and the channel type multi-temperature zone heating device, the substrate in the reaction vessel undergoes a temperature rise and fall process to complete the thermochemical reaction required to fabricate the semiconductor thin film solar cell.
可选的， 所述生产线固定不动， 利用控制部件控制旋转机构驱动所 述通道式多温区加热装置沿着所述生产线移动。 可选的， 所述通道式多温区加热装置固定不动， 控制部件控制旋转 机构驱动所述生产线移动。 Optionally, the production line is fixed, and the control unit controls the rotating mechanism to drive the channel type multi-temperature zone heating device to move along the production line. Optionally, the channel type multi-temperature zone heating device is fixed, and the control component controls the rotation mechanism to drive the production line to move.
可选的， 所述生产线为圆形， 所述通道式多温区加热装置为圆弧形。 可选的， 所述生产线为类似田径场形状的直线与圆相结合的形式， 或任何圆弧与直线首位相连的形式， 所述通道式多温区加热装置为直线 型或圆弧形。  Optionally, the production line is circular, and the channel type multi-temperature zone heating device has a circular arc shape. Optionally, the production line is in the form of a combination of a straight line and a circle similar to the shape of the track field, or any arc connected to the first position of the straight line, and the channel type multi-temperature zone heating device is linear or arc-shaped.
可选的， 所述复数个固定温区包括升温区、 合金化区、 硒化区、 硫 化区和退火区。  Optionally, the plurality of fixed temperature zones includes a temperature rising zone, an alloying zone, a selenization zone, a sulfurization zone, and an annealing zone.
可选的， 所述反应容器为耐温耐腐蚀的石英玻璃或金属盒体。  Optionally, the reaction vessel is a temperature resistant and corrosion resistant quartz glass or metal case.
可选的， 所述物理镀膜法包括真空热镀膜法、 磁控溅射法、 电化学 镀膜法或湿法涂覆法。  Optionally, the physical coating method comprises a vacuum hot coating method, a magnetron sputtering method, an electrochemical coating method or a wet coating method.
可选的， 所述湿法涂覆法包括旋涂、 喷涂、 丝印、 滴涂、 浸涂等印 刷方法。  Optionally, the wet coating method comprises a printing method such as spin coating, spray coating, silk screen printing, dripping coating, dip coating or the like.
与现有技术相比， 本发明具有以下优点：  Compared with the prior art, the present invention has the following advantages:
本发明的半导体薄膜太阳能电池的制造系统和方法为具有升降温过 程的热化学反应提供了新的和更为优良的工艺手段。 本发明的半导体薄 膜太阳能电池的制造系统采用通道式多温区加热装置， 该装置具有多个 其温度根据工艺要求而设定的固定温区， 每个温区内温度恒定。 反应容 器通过旋转机构与通道式多温区加热装置做相对旋转运动， 反应容器按 照预先设定的速度依次进入通道式多温区加热装置， 顺序经过每个温度 恒定的温区后再走出通道式多温区加热装置， 这样， 每个反应容器内的 需要进行热化学反应的衬底、 基材或玻璃基片都能够连续、 依次经过每 个温度恒定的温区， 在每个恒温区内进行相应的、 温度波动最小的工艺 操作。 经过了每个恒温区之后也就完成了与升降温工艺条件相对应的整 个热化学反应过程。 本发明的半导体薄膜太阳能电池的制造系统和方法 避免了传统的在同一个反应室内进行变温操作时升降温过程的温度波动 和冲击， 使每个反应容器内的衬底、 基材或玻璃基片得以平稳地获得升 / 降温， 热化学反应条件更加优化， 特别适用于 CIGS薄膜太阳能电池制造 过程中的硒化热化学反应。 而且， 由于没有了升降温过程， 大大节省了 升降温所需的时间， 提高了生产效率。 此外， 本发明半导体薄膜太阳能 电池的制造系统的旋转机构可放置众多反应容器， 每个反应容器中又可 放置众多玻璃基片等基材， 配合进入通道式多温区加热装置之前的装片 操作和走出多温区加热装置之后的卸片操作， 使本发明能够高产量、 连 续不间断地制造 CIGS多晶薄膜， 极大地提高了产能， 符合产业化生产的 需要。 The system and method for fabricating a semiconductor thin film solar cell of the present invention provides a new and superior process for the thermochemical reaction with a temperature rise and fall process. The manufacturing system of the semiconductor thin film solar cell of the present invention adopts a channel type multi-temperature zone heating device, and the device has a plurality of fixed temperature zones whose temperatures are set according to process requirements, and the temperature in each temperature zone is constant. The reaction vessel is rotated relative to the channel type multi-temperature zone heating device by a rotating mechanism, and the reaction vessel sequentially enters the channel type multi-temperature zone heating device according to a preset speed, sequentially passes through each temperature zone with constant temperature, and then exits the channel type. Multi-temperature zone heating device, thus, in each reaction vessel The substrate, the substrate or the glass substrate which is required to undergo the thermochemical reaction can continuously and sequentially pass through each of the constant temperature zones, and the corresponding process with the least temperature fluctuation is performed in each constant temperature zone. After each constant temperature zone, the entire thermochemical reaction process corresponding to the temperature rise and fall process conditions is completed. The manufacturing system and method for the semiconductor thin film solar cell of the present invention avoids the temperature fluctuation and impact of the conventional temperature rise and fall process during the temperature change operation in the same reaction chamber, so that the substrate, the substrate or the glass substrate in each reaction container It is able to smoothly obtain the rise/fall temperature and optimize the thermochemical reaction conditions, which is especially suitable for the selenization thermochemical reaction in the manufacturing process of CIGS thin film solar cells. Moreover, since there is no temperature rise and fall process, the time required for the temperature rise and fall is greatly saved, and the production efficiency is improved. In addition, the rotating mechanism of the manufacturing system of the semiconductor thin film solar cell of the present invention can place a plurality of reaction vessels, and each of the reaction vessels can be placed with a plurality of substrates such as glass substrates, and the loading operation before entering the channel type multi-temperature zone heating device And the unloading operation after exiting the multi-zone heating device enables the invention to manufacture CIGS polycrystalline film with high yield and continuous uninterrupted production, which greatly improves the production capacity and meets the needs of industrial production.
附图说明 DRAWINGS
通过附图中所示的本发明的优选实施例的更具体说明， 本发明的上 述及其它目的、 特征和优势将更加清晰。 在全部附图中相同的附图标记 指示相同的部分。 并未刻意按比例绘制附图， 重点在于示出本发明的主 旨 图 1为说明一般在同一反应室内执行变温工艺的温度曲线； 图 2 为根据本发明第一实施例的半导体薄膜太阳能电池制造系统示 意图； The above and other objects, features and advantages of the present invention will become more apparent from the <RTIgt; The same reference numerals are used throughout the drawings to refer to the same parts. The drawings are not intended to be drawn to scale, the emphasis is on illustrating the subject matter of the present invention. FIG. 1 is a temperature profile illustrating a temperature change process generally performed in the same reaction chamber; FIG. 2 is a semiconductor thin film solar cell manufacturing system according to a first embodiment of the present invention. Show Intention
图 3为说明本发明的变温工艺的温度曲线；  Figure 3 is a temperature chart illustrating the temperature change process of the present invention;
图 4为根据本发明第二实施例的半导体薄膜太阳能电池制造系统示 意图。  Fig. 4 is a view showing a semiconductor thin film solar cell manufacturing system according to a second embodiment of the present invention.
所述示图是说明性的， 而非限制性的， 在此不能过度限制本发明的 保护范围。  The illustrations are illustrative and not limiting, and the scope of the invention is not to be unduly limited.
具体实施方式 detailed description
为使本发明的上述目的、 特征和优点能够更加明显易懂， 下面结合 附图对本发明的具体实施方式做详细的说明。 在下面的描述中阐述了很 多具体细节以便于充分理解本发明。 但是本发明能够以很多不同于在此 描述的其它方式来实施， 本领域技术人员可以在不违背本发明内涵的情 况下做类似推广。 特别说明的是， 本发明不但特别适用于 CIGS多晶薄膜 太阳能电池的硒化热化学反应， 而且适用于其他任何需要变温的热化学 反应。 因此本发明不受下面公开的具体实施例的限制。  The above described objects, features and advantages of the present invention will become more apparent from the aspects of the appended claims. Numerous specific details are set forth in the description which follows to provide a thorough understanding of the invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art can make similar promotion without departing from the scope of the present invention. In particular, the present invention is not only particularly suitable for the selenization thermochemical reaction of CIGS polycrystalline thin film solar cells, but also for any other thermochemical reaction requiring temperature change. The invention is therefore not limited by the specific embodiments disclosed below.
根据制备 CIGS多晶薄膜太阳能电池的硒化热化学反应的要求不同， 热化学反应的温度及某一特定温度下所经历的时间也不同。 图 1 为说明 一般在同一反应室内执行变温工艺的温度曲线。 具体而言， 图 1 是进行 铜铟镓硒化热化学反应的一种温度曲线， 如图 1 所示， 在镀钼的玻璃基 片上蒸镀一层铜铟（1 : 1 )金属预制体， 之后将玻璃基片升温至 150°C并 保持 5分钟以去除所吸附的水或氧。 然后基片在反应容器中被进一歩加 热至 320°C并保持 5分钟以使铜-铟金属充分合金化。 之后反应容器在通 入 ¾Se的情况下升温至 420 °C并保持 20分钟以促使铜-铟合金硒化形成 初始铜铟硒化物半导体薄膜。 为了制备适合于太阳能电池的薄膜， 有必 要对所形成的初始铜铟硒化物进一歩升温至 550 °C并保持 15分钟以促使 微晶性铜铟硒化物薄膜长成大粒多晶铜铟硒化物薄膜。 经过约 25分钟的 退火降温后（小于 80°C )， 热硒化反应所形成的铜铟硒薄膜基片即已形成 并可从反应容器中取出为下一歩工艺备用。 实现图 1所示的升 /降温热化 学反应的一般途径是将装有基片的反应容器置于一个反应室内， 利用加 热元件通过电功率控制使反应室内的温度升高或降低， 从而使反应容器 内的基片经历变温过程。 然而， 由于电功率控制的加热元件随时间按工 艺要求变温时， 会不可避免地产生大幅度的温度冲击和波动 （ 25 °C， 如 Π、 Τ2、 Τ3和 Τ4处的曲线所示）。 这种大幅度的温度振荡往往导致最 终太阳能电池单片内不同区域的质量不均匀， 以及片与片之间的质量差 异， 甚至是玻璃基片的变形。 所有这些都将导致低良率而影响高量产。 Depending on the requirements for the thermochemical reaction of selenization for the preparation of CIGS polycrystalline thin film solar cells, the temperature of the thermochemical reaction and the time elapsed at a particular temperature are also different. Figure 1 is a graph showing the temperature profile of a temperature swing process typically performed in the same reaction chamber. Specifically, FIG. 1 is a temperature profile for performing a thermochemical reaction of copper indium gallium selenide. As shown in FIG. 1, a copper indium (1:1) metal preform is deposited on a molybdenum-plated glass substrate. The glass substrate was then heated to 150 ° C and held for 5 minutes to remove adsorbed water or oxygen. The substrate was then heated in a reaction vessel to 320 ° C and held for 5 minutes to fully alloy the copper-indium metal. After the reaction container is in communication The temperature was raised to 420 ° C in the case of 3⁄4 Se and held for 20 minutes to promote selenization of the copper-indium alloy to form an initial copper indium selenide semiconductor film. In order to prepare a film suitable for a solar cell, it is necessary to heat the initial copper indium selenide formed to 550 ° C for 15 minutes to promote the growth of the microcrystalline copper indium selenide film into a large polycrystalline copper indium selenide film. film. After annealing for about 25 minutes (less than 80 ° C), the copper indium selenide film substrate formed by the thermal selenization reaction is formed and can be taken out from the reaction vessel for use in the next process. The general way to achieve the rising/lowering thermochemical reaction shown in Figure 1 is to place the reaction vessel containing the substrate in a reaction chamber, and the temperature of the reaction chamber is raised or lowered by electric power control by means of a heating element, thereby making the reaction vessel The inner substrate undergoes a temperature change process. However, as electrical power-controlled heating elements become temperature-dependent over time, large temperature shocks and fluctuations (25 °C, as shown by the curves at Π, Τ2, Τ3, and Τ4) are inevitably generated. This large temperature oscillation often results in uneven quality in different regions of the final solar cell, as well as mass differences between the sheets, even the deformation of the glass substrate. All of this will result in low yields and high yields.
本发明的半导体薄膜太阳能电池的制造系统和方法为具有升降温过 程的热化学反应， 特别是本文关注的硒化热化学反应提供了新的和更为 优良的工艺手段。 图 2 为根据本发明第一实施例的半导体薄膜太阳能电 池制造系统示意图。 如图 2所示， 本发明的半导体薄膜太阳能电池制造 系统包括一个长径比很大的通道式多温区加热装置 70 ; 多个用于容纳太 阳能薄膜玻璃基片的热化学反应容器 71 ; 旋转机构 72， 通过连接杆 78 带动反应容器 71在轨道上运行； 用于控制气氛 （如真空、 惰性气体或反 应气体）的供气站 73 ; 用于控制通道式多温区加热装置 70和热化学反应 容器 71之间相对运动速度的控制站 74; 用于人工或自动向反应容器 71 内装片的装片区 75和从反应容器 71中取出基片的卸片区 76。 此外， 为 顾及环境和操作人员的安全， 本发明的半导体薄膜太阳能电池制造系统 还可包括尾气处理系统和相应的安全传感器检测器。 The manufacturing system and method for the semiconductor thin film solar cell of the present invention is a thermochemical reaction having a temperature rise and fall process, and in particular, the selenization thermochemical reaction of interest herein provides a new and superior process. 2 is a schematic view showing a semiconductor thin film solar cell manufacturing system according to a first embodiment of the present invention. As shown in FIG. 2, the semiconductor thin film solar cell manufacturing system of the present invention comprises a channel type multi-temperature zone heating device 70 having a large aspect ratio; a plurality of thermochemical reaction vessels 71 for accommodating a solar film glass substrate; The mechanism 72 drives the reaction vessel 71 to run on the rail by the connecting rod 78; the gas supply station 73 for controlling the atmosphere (such as vacuum, inert gas or reaction gas); for controlling the channel type multi-temperature zone heating device 70 and thermochemistry Reaction A control station 74 for the relative movement speed between the containers 71; a loading area 75 for manually or automatically loading the inside of the reaction container 71; and a discharge area 76 for taking out the substrate from the reaction container 71. Furthermore, to meet environmental and operator safety, the semiconductor thin film solar cell manufacturing system of the present invention may further include an exhaust gas treatment system and a corresponding safety sensor detector.
根据本发明的实施例， 对应图 1 中变温工艺的温度曲线， 在所述通 道式多温区加热装置 70内设置多个特定温度的温区， 反应容器 71按箭 头方向依次顺序通过各个温区。 即 Π区、 T2区、 T3区、 T4区和 T5区， 每个温区内温度恒定。 分别为， Π区： 去湿脱氧区， 温度设定为 150°C， 在这个温区内， 玻璃基片在真空下的反应容器内被加热至 150°C ; T2区： 合金化区， 温度设定为 320°C， 在这个温区内， 玻璃基片上的预制体金属 进一歩合金化； T3 区： 硒化热化学反应区， 温度设定为 420 °C， 在这个 温区内， 预制体硒化反应成铜铟硒化物半导体薄膜； T4区： 结晶完善区， 温度设定为 550°C， 在这个温区内， 半导体薄膜结晶晶粒形成大晶粒 l m) ; T5 区： 退火降温区， 温度设定为 80°C左右， 在这个温区内， 玻 璃基片降温退火以备出片。  According to an embodiment of the present invention, corresponding to the temperature profile of the variable temperature process in FIG. 1, a plurality of temperature zones of a specific temperature are disposed in the channel type multi-temperature zone heating device 70, and the reaction vessels 71 sequentially pass through the respective temperature zones in the order of the arrow direction. . That is, the helium zone, the T2 zone, the T3 zone, the T4 zone and the T5 zone, and the temperature in each temperature zone is constant. Respectively, Π zone: dehumidification deoxidation zone, the temperature is set to 150 ° C, in this temperature zone, the glass substrate is heated to 150 ° C in the reaction vessel under vacuum; T2 zone: alloying zone, temperature Set to 320 ° C, in this temperature zone, the preformed metal on the glass substrate is alloyed; T3 zone: Selenization thermochemical reaction zone, temperature set to 420 °C, prefabricated in this zone The selenization reaction is carried out into a copper indium selenide semiconductor film; T4 region: a crystalline perfect region, the temperature is set to 550 ° C, in this temperature region, the crystal grains of the semiconductor thin film form large grains lm); T5 region: annealing and cooling In the zone, the temperature is set to about 80 ° C. In this temperature zone, the glass substrate is cooled and annealed to prepare a sheet.
通道式多温区加热装置 70内可以容纳很多彼此间隔的热化学反应容 器 71， 较为合适的数量为 3000个， 一般为 5〜500个， 显然， 根据通道 式多温区加热装置 70所覆盖的反应容器 71的数量， 其长度可相应变化。 因此无论通道式多温区加热装置 70的长度为多少， 均在本发明的保护范 围内。 较合适的长度为 5〜500米， 长度越长， 所容纳或覆盖的反应容器 越多， 单位时间内的产量越大。 通道式多温区加热装置 70内固定温区的 数量根据实际的工艺要求设定， 根据反应时间的要求设定每个温区的长 度。 根据本实施例， 玻璃基片在 Π区、 T2区、 T3区、 T4区和 T5区内的 停留时间分别为 5分钟、 5分钟、 20分钟、 15分钟和 15分钟。 Π区、 T2区、 T3区、 T4区和 T5区的长度根据基片的停留时间而定， 通过控制 站 74控制旋转机构 72转动的速度， 以合适的速度令反应容器 71通道内 的各个温区中运行， 以满足工艺要求。 图 3 为说明本发明的变温工艺的 温度曲线。 由图 3可以看出， 本发明的变温过程无需升降温， 而是逐歩 平稳经过各个不同温区， 每个温区温度基本恒定， 基本不存在温度波动。 当载有预制体的反应容器 71以一定的速度缓慢通过各个温区时， 则实现 了升降温过程， 反应容器 71内的玻璃基片在升降温过程中的温度波动趋 于最小 （小于 3〜5 °C )。 而且省去了常规加热的升降温时间， 提高了生产 效率。 The channel type multi-zone heating device 70 can accommodate a plurality of thermochemical reaction vessels 71 spaced apart from each other, and a suitable number is 3000, generally 5 to 500, apparently covered by the channel type multi-zone heating device 70. The number of reaction vessels 71, the length of which can vary accordingly. Therefore, regardless of the length of the channel type multi-zone heating device 70, it is within the scope of the present invention. A suitable length is 5 to 500 meters. The longer the length, the more reaction vessels are accommodated or covered, and the larger the yield per unit time. Channel type multi-temperature zone heating device 70 fixed temperature zone The quantity is set according to the actual process requirements, and the length of each temperature zone is set according to the reaction time requirement. According to this embodiment, the residence time of the glass substrate in the crotch region, the T2 region, the T3 region, the T4 region, and the T5 region was 5 minutes, 5 minutes, 20 minutes, 15 minutes, and 15 minutes, respectively. The lengths of the crotch region, the T2 region, the T3 region, the T4 region and the T5 region depend on the residence time of the substrate, and the speed of rotation of the rotating mechanism 72 is controlled by the control station 74 to cause each temperature in the passage of the reaction vessel 71 at an appropriate speed. Run in the zone to meet process requirements. Figure 3 is a graph showing the temperature profile of the temperature change process of the present invention. As can be seen from FIG. 3, the temperature change process of the present invention does not require temperature rise and fall, but smoothly passes through various different temperature zones, and the temperature of each temperature zone is substantially constant, and there is substantially no temperature fluctuation. When the reaction vessel 71 carrying the preform slowly passes through the respective temperature zones at a certain speed, the temperature rise and fall process is realized, and the temperature fluctuation of the glass substrate in the reaction vessel 71 during the temperature rise and fall process tends to be minimum (less than 3~) 5 °C). Moreover, the temperature rise and fall time of the conventional heating is omitted, and the production efficiency is improved.
本发明的通道式多温区加热装置 70包括加热元件、 保温炉体、 控温 部件， 运动导轨等。 加热元件可采用燃烧点火加温或更为方便的电加热 加温。 其它的加热方式如感应加热、 微波加热等也可使用。 因化学反应 通常在 20(T600°C， 通道式多温区加热装置 70需要良好地保温， 所适合 的材料一般可为任何兼具力学强度和隔热的材料， 例如陶瓷、 玻璃、 砖 瓦、 多层石墨或陶瓷纤维棉等。 控温部件一般由温度的检测、 显示、 设 定及控制等部分组成。 本领域中的一般技术人员都可以建立并实现这样 的控温部件。  The channel type multi-temperature zone heating device 70 of the present invention includes a heating element, a holding furnace body, a temperature control member, a moving rail, and the like. The heating element can be heated by combustion ignition or more convenient electric heating. Other heating methods such as induction heating, microwave heating, etc. can also be used. Since the chemical reaction is usually at 20 (T600 ° C, the channel type multi-zone heating device 70 needs to be well insulated, the suitable material can generally be any material with both mechanical strength and thermal insulation, such as ceramics, glass, brick, Multi-layer graphite or ceramic fiber cotton, etc. Temperature-control components are generally composed of temperature detection, display, setting, and control, etc. Those skilled in the art can establish and implement such temperature-control components.
需要说明的是， 上述各个温区的设定是制备铜铟硒化物半导体薄膜 的一个例子， 根据不同的半导体薄膜要求， 各个特定的温度可相应改变， 均在本发明的保护范围。 It should be noted that the setting of each of the above temperature zones is to prepare a copper indium selenide semiconductor film. As an example, depending on the requirements of the semiconductor film, each specific temperature can be changed accordingly, and is within the scope of the present invention.
通道式多温区加热装置 70和硒化反应容器 71之间产生相对运动的 一种方式是把多个反应容器 71安装在耐热材料轴或球， 如氧化铝， 或瓷 轴 （或瓷球）在轨道上滚动使反应容器 71运动通过通道式多温区加热装 置 70。产生相对运动的另一种方式是在固定硒化反应容器不动的情况下， 使通道式多温区加热装置运动而实现省降温过程。  One way to create relative motion between the channel type multi-zone heating device 70 and the selenization reaction vessel 71 is to mount a plurality of reaction vessels 71 on a heat resistant material shaft or ball, such as alumina, or a ceramic shaft (or ceramic ball). Rolling on the track moves the reaction vessel 71 through the channel type multi-zone heating device 70. Another way to generate relative motion is to move the channel-type multi-temperature zone heating device to achieve a cooling process while the stationary selenization reaction vessel is stationary.
图 4为根据本发明第二实施例的半导体薄膜太阳能电池制造系统示 意图。 图 4所示即为本发明优选实施例的通道式多温区加热装置移动的 半导体薄膜太阳能电池制造系统。 如图 4所示， 本实施例中， 控制部件 控制旋转机构驱动通道式多温区加热装置 80在轨道 82上以一定速度缓 慢移动， 如箭头所示， 热化反应容器 81依次顺序经过各个恒温区， 气源 区 87为反应容器 81提供各种气氛， 真空系统 86提供真空环境， 操作人 员 85执行装片和卸片的操作， 尾气处理系统 84对废气进行处理。 由于 硒化反应容器 81通常连接有真空、 惰性气体、 反应气体和尾气出口等管 路， 更为适宜的方式是使通道式多温区加热装置 80移动。 因此， 在通道 式多温区加热装置 80下安装导轨 82使其象有轨电动火车或内燃机车一 样运行为本发明优选的运动方式。  Fig. 4 is a view showing a semiconductor thin film solar cell manufacturing system according to a second embodiment of the present invention. Fig. 4 is a view showing a semiconductor thin film solar cell manufacturing system in which a channel type multi-zone heating device is moved according to a preferred embodiment of the present invention. As shown in FIG. 4, in this embodiment, the control unit controls the rotating mechanism to drive the channel type multi-temperature zone heating device 80 to slowly move on the track 82 at a certain speed. As indicated by the arrows, the heating reaction container 81 sequentially passes through the respective constant temperature. The gas source zone 87 provides various atmospheres for the reaction vessel 81, the vacuum system 86 provides a vacuum environment, the operator 85 performs the loading and unloading operations, and the exhaust gas treatment system 84 treats the exhaust gases. Since the selenization reaction vessel 81 is usually connected to a pipe such as a vacuum, an inert gas, a reaction gas, and an exhaust gas outlet, it is more preferable to move the channel type multi-temperature zone heating device 80. Therefore, the guide rails 82 are mounted under the channel type multi-zone heating device 80 to operate as a railed electric train or diesel locomotive as a preferred mode of motion of the present invention.
由于采用固定温区的通道式多温区加热装置， 当其与硒化反应容器 作相对运动时， 炉体内的硒化反应容器得以获得升降温。 因为炉体内的 各个温区温度恒定， 故而每个反应容器所经历的温度波动最小。 此处的 温度波动是指设定温度和实际温度之间的差异。 当一个加热元件要随时 间而调节不同的温度时， 不可避免地要产生温度冲击或振荡， 导致设定 值与实际值之间的差异。而当一个加热元件无需随时间调节不同温度时， 此时的加热元件维持一个给定热量的稳定态， 使设定值和实际值之间的 温度差异最小， 最有利于达到高良率生产。 Due to the channel type multi-temperature zone heating device in the fixed temperature zone, when it is moved relative to the selenization reaction vessel, the selenization reaction vessel in the furnace body can be heated and lowered. Since the temperature in each temperature zone of the furnace is constant, the temperature fluctuation experienced by each reaction vessel is minimal. Here Temperature fluctuation is the difference between the set temperature and the actual temperature. When a heating element has to adjust different temperatures over time, it is inevitable to generate a temperature shock or oscillation, resulting in a difference between the set value and the actual value. When a heating element does not need to adjust different temperatures over time, the heating element at this time maintains a steady state of a given heat, minimizing the temperature difference between the set value and the actual value, and is most advantageous for achieving high yield production.
本发明并不排除通道式多温区加热装置与硒化反应装置之间作直线 运动， 即直线运动式通道式多温区加热装置。 为了达到连续不间断高量 产， 最优选的方式是反应容器首位相连， 排列为圆形生产线， 通道式多 温区加热装置为圆弧形， 如图 2所示。 也可以是田径场形状的直线与圆 相结合， 或是任何圆弧与直线首位相连的生产线。 首尾相连的最大好处 是反应容器和通道式多温区加热装置之间能够循环往复、 周而复始地连 续运行， 不间断生产。  The present invention does not exclude linear motion between the channel type multi-temperature zone heating device and the selenization reaction device, that is, a linear motion channel type multi-temperature zone heating device. In order to achieve continuous uninterrupted high-volume production, the most preferred way is that the reaction vessels are connected in the first place and arranged in a circular production line, and the channel-type multi-temperature zone heating device has a circular arc shape, as shown in FIG. It can also be a combination of a straight line in the shape of a track field and a circle, or a production line in which any arc is connected to the first position of the line. The biggest benefit of the end-to-end connection is that the reaction vessel and the channel-type multi-zone heating unit can be reciprocated and continuously operated continuously, without interruption.
根据生产量的要求不同， 首尾相连的生产线的长度可为 2CT500米， 较适合的总长度为 3CT300米。 考虑到装片和卸片， 首尾相连的生产线设 置有装片区， 用于装入预制体玻璃基片并进行必要的检漏等检测， 安全 检查及热化学预备工作； 卸片区， 用于基片降温和开盒卸片； 通道式多 温区加热装置所在的区域可称为热化学反应区或硒化区， 用于进行有效 的热化学反应或硒化反应。  Depending on the requirements of the production volume, the length of the end-to-end production line can be 2CT500m, and the suitable total length is 3CT300m. Considering the loading and unloading, the end-to-end production line is provided with a loading area for loading the preformed glass substrate and performing necessary leak detection, safety inspection and thermochemical preparation; unloading area, for substrate Cooling and unpacking; The area where the channel type multi-temperature zone heating device is located may be called a thermochemical reaction zone or a selenization zone for effective thermochemical reaction or selenization reaction.
反应容器包括耐温耐化学腐蚀的腔体和用于玻璃基片装卸的门， 以 及用于抽真空和控制气氛的进出管路。 较为适宜的腔体和门的材料可采 用耐温耐腐蚀的不锈钢或石英玻璃， 刚玉等。 考虑到力学强度、 成本和 加工简便， 优选为不锈钢。 为了增加温度的平缓性及减少铁对半导体表 面的可能污染， 反应容器内衬可选用石英玻璃、 陶瓷或石墨作为内衬。 The reaction vessel includes a temperature and chemical resistant chamber and a door for loading and unloading the glass substrate, and an inlet and outlet line for evacuating and controlling the atmosphere. Suitable cavity and door materials can be made of temperature-resistant and corrosion-resistant stainless steel or quartz glass, corundum and the like. Considering mechanical strength, cost and The processing is simple, preferably stainless steel. In order to increase the temperature temperability and reduce the possible contamination of the semiconductor surface by iron, the reaction vessel lining may be made of quartz glass, ceramic or graphite as an inner liner.
许多材料都可以作为薄膜太阳能电池的玻璃基片， 如钠 -碱玻璃具有 成本低的特点， 且钠-碱玻璃中钠元素还可微量掺杂铜铟硒或铜铟镓硒， 促使微晶的长大， 有利于电池性能的提高。 为了形成背电极导电层、 金 属层， 如钼、 钛、 铬或其它合金， 可采用物理镀膜的方法， 如磁控溅射、 真空蒸镀法， 获得兼具导电和反光功能的背电极。 根据本发明， 基片还 可以使用金属柔性基材， 如不锈钢或铝箔等。 为便于电池模板的叠层串 接， 通常先在金属柔性基材表面生长一层电绝缘材料膜， 如二氧化硅， 然后再利用物理镀膜的方式形成反光背电极。 除此之外， 还可以使用聚 合物薄膜作为基材， 考虑到耐热要求， 目前适合的聚合物为聚酰亚胺、 聚酰醚胺、 聚砜亚胺等。 反光导电电极金属可镀在聚合物一面， 或更好 是镀在聚合物的两面， 以增加耐热性， 避免基材变形。  Many materials can be used as glass substrates for thin film solar cells, such as sodium-alkali glass, which has low cost, and the sodium element in sodium-alkali glass can also be doped with copper indium selenide or copper indium gallium selenide to promote microcrystalline Growing up is good for battery performance. In order to form a back electrode conductive layer, a metal layer such as molybdenum, titanium, chromium or other alloy, a physical coating method such as magnetron sputtering or vacuum evaporation may be employed to obtain a back electrode having both conductive and reflective functions. According to the present invention, the substrate may also use a metal flexible substrate such as stainless steel or aluminum foil or the like. In order to facilitate the lamination of the battery template, a film of an electrically insulating material, such as silicon dioxide, is first grown on the surface of the metal flexible substrate, and then a reflective back electrode is formed by physical plating. In addition, a polymer film can also be used as the substrate, and in view of heat resistance requirements, currently suitable polymers are polyimide, polyetheretheramine, polysulfonymine, and the like. The reflective conductive electrode metal may be plated on one side of the polymer or, more preferably, on both sides of the polymer to increase heat resistance and avoid deformation of the substrate.
本发明所指的半导体是指 IB-IIIA-VIA,其中典型如 CuInS2、CuInSe2、 Culru— xG Se2、 Culru— XS2、 Culru— xG Se2— ySy， （x=0〜l， y=0〜2)。 本发明所指 的半导体还可以是 III-V半导体， 如 GaAs, InP等。 为获得这些化合物 半导体， 可先制得它们的前驱体， 即含所有或大部分元素的金属或化合 物前驱体薄膜， 然后再把这些前驱体加热， 同时通入反应气体， 如 H2S、 H2Se、 ¾P、 ¾AS等， 形成化合物半导体。 The semiconductor referred to in the present invention means IB-IIIA-VIA, and typically such as CuInS 2 , CuInSe 2 , Culru- x G Se 2 , Culru- X S 2 , Culru- x G Se 2 — y S y , (x= 0~l, y=0~2). The semiconductor referred to in the present invention may also be a III-V semiconductor such as GaAs, InP or the like. In order to obtain these compound semiconductors, their precursors, that is, metal or compound precursor films containing all or most of the elements, may be prepared, and then these precursors are heated while introducing a reaction gas such as H 2 S, H 2 . Se, 3⁄4P, 3⁄4AS, etc. form a compound semiconductor.
原则上所有薄膜制备方法皆可作为前驱体的制造方法， 较为适宜的 方法有磁控溅射、 蒸镀、 电镀、 纳米粒子涂覆， 甚或溶液涂覆印刷法。 以上所述， 仅是本发明的较佳实施例而已， 并非对本发明作任何形 式上的限制。 任何熟悉本领域的技术人员， 在不脱离本发明技术方案范 围情况下， 都可利用上述揭示的技术内容对本发明技术方案做出许多可 能的变动和修饰， 或修改为等同变化的等效实施例。 因此， 凡是未脱离 本发明技术方案的内容， 依据本发明的技术实质对以上实施例所做的任 何简单修改、 等同变化及修饰， 均仍属于本发明技术方案的保护范围内。 In principle, all film preparation methods can be used as a precursor manufacturing method, and a suitable method is magnetron sputtering, evaporation, electroplating, nanoparticle coating, or even solution coating printing. The above description is only a preferred embodiment of the invention and is not intended to limit the invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention by using the above-disclosed technical contents, or modify equivalent embodiments of equivalent changes without departing from the scope of the technical solutions of the present invention. . Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments in accordance with the technical spirit of the present invention are still within the scope of the present invention.

Claims

权利 要求 Rights request
1、 一种半导体薄膜太阳能电池的制造系统， 其特征在于包括： 具有复数个固定温区的通道式多温区加热装置；  What is claimed is: 1. A semiconductor thin film solar cell manufacturing system, comprising: a channel type multi-temperature zone heating device having a plurality of fixed temperature zones;
由复数个可调节气氛的热化学反应容器组成的生产线； 以及 旋转机构和控制部件， 所述控制部件控制所述旋转机构驱动所述生 产线上的热化学反应容器顺序通过所述通道式多温区加热装置的复数个 固定温区。  a production line consisting of a plurality of thermochemical reaction vessels capable of adjusting an atmosphere; and a rotating mechanism and a control member, the control member controlling the rotating mechanism to drive the thermochemical reaction vessels on the production line sequentially through the channel type multi-temperature zone A plurality of fixed temperature zones of the heating device.
2、 如权利要求 1所述的系统， 其特征在于： 所述生产线固定不动， 所述控制部件控制所述旋转机构驱动所述通道式多温区加热装置沿着生 产线移动。  The system according to claim 1, wherein: said production line is stationary, and said control means controls said rotating mechanism to drive said channel type multi-temperature zone heating means to move along the production line.
3、 如权利要求 1所述的系统， 其特征在于： 所述通道式多温区加热 装置固定不动， 所述控制部件控制所述旋转机构驱动生产线移动。  3. The system of claim 1 wherein: said channelized multi-temperature zone heating device is stationary, said control component controlling said rotating mechanism to drive production line movement.
4、 如权利要求 2或 3所述的系统， 其特征在于： 所述生产线为圆形， 所述通道式多温区加热装置为圆弧形。  4. The system according to claim 2 or 3, wherein: the production line is circular, and the channel type multi-temperature zone heating device has a circular arc shape.
5、 如权利要求 2或 3所述的系统， 其特征在于： 所述生产线为类似田 径场形状的直线与圆形相结合的形式， 或任何圆弧与直线首位相连的形 式。  5. System according to claim 2 or 3, characterized in that the production line is in the form of a combination of a straight line and a circular shape resembling the shape of a field, or any arc connected to the first position of the straight line.
6、 如权利要求 5所述的系统， 其特征在于： 所述通道式多温区加热 装置为直线型或圆弧形。  6. The system of claim 5 wherein: said channel type multi-temperature zone heating means is linear or arcuate.
7、 如权利要求 1所述的系统， 其特征在于： 所述气氛包括硒化氢、 硫化氢、 有机硒化物、 有机硫化物、 高温硒蒸气、 高温硫蒸气， 以及惰 性气体中的两种或多种的混合气体。 7. The system of claim 1 wherein: said atmosphere comprises hydrogen selenide, hydrogen sulfide, organic selenide, organic sulfide, high temperature selenium vapor, high temperature sulfur vapor, and inert A mixed gas of two or more kinds of gaseous gases.
8、 一种半导体薄膜太阳能电池的制造方法， 其特征在于包括： 在导电电极上通过物理镀膜法制备化合物半导体前驱体；  8. A method of fabricating a semiconductor thin film solar cell, comprising: preparing a compound semiconductor precursor by a physical plating method on a conductive electrode;
把载有所述化合物半导体前驱体的基片置于一气氛可调的反应容 器；  The substrate carrying the compound semiconductor precursor is placed in an atmosphere-adjustable reaction vessel;
由复数个所述反应容器组成的生产线依次经过具有复数个固定温区 的通道式多温区加热装置；  a production line consisting of a plurality of said reaction vessels sequentially passes through a channel type multi-temperature zone heating device having a plurality of fixed temperature zones;
随着所述生产线与所述通道式多温区加热装置的相对移动， 所述反 应容器内的基片经历升降温过程而完成制造半导体薄膜太阳能电池所需 的热化学反应。  With the relative movement of the production line and the channel type multi-temperature zone heating device, the substrate in the reaction vessel undergoes a temperature rise and fall process to complete the thermochemical reaction required to fabricate the semiconductor thin film solar cell.
9、 如权利要求 8所述的方法， 其特征在于： 所述生产线固定不动， 利用控制部件控制旋转机构驱动所述通道式多温区加热装置沿着所述生 产线移动。  9. The method according to claim 8, wherein: said production line is stationary, and said control unit controls said rotating mechanism to drive said channel type multi-temperature zone heating device to move along said production line.
10、 如权利要求 8所述的方法， 其特征在于： 所述通道式多温区加热 装置固定不动， 控制部件控制旋转机构驱动所述生产线移动。  10. The method of claim 8 wherein: said channelized multi-zone heating means is stationary and said control means controls the rotating mechanism to drive said line movement.
11、如权利要求 9或 10所述的方法，其特征在于：所述生产线为圆形， 所述通道式多温区加热装置为圆弧形。  A method according to claim 9 or 10, wherein said production line is circular, and said channel type multi-temperature zone heating means has a circular arc shape.
12、 如权利要求 9或 10所述的方法， 其特征在于： 所述生产线为类似 田径场形状的直线与圆相结合的形式， 或任何圆弧与直线首位相连的形 式， 所述通道式多温区加热装置为直线型或圆弧形。  12. The method according to claim 9 or 10, wherein: the production line is in the form of a combination of a straight line and a circle similar to the shape of an athletic field, or a form in which any arc is connected to the first position of the straight line. The heating zone heating device is linear or circular.
13、 如权利要求 8所述的方法， 其特征在于： 所述复数个固定温区包 括升温区、 合金化区、 硒化区、 硫化区和退火区。 13. The method of claim 8, wherein: the plurality of fixed temperature zones comprises a temperature rising zone, an alloying zone, a selenization zone, a vulcanization zone, and an annealing zone.
14、 如权利要求 8所述的方法， 其特征在于： 所述反应容器为耐温耐 腐蚀的石英玻璃或金属盒体。 14. The method of claim 8 wherein: said reaction vessel is a temperature resistant corrosion resistant quartz glass or metal casing.
15、 如权利要求 8所述的方法， 其特征在于： 所述物理镀膜法包括真 空热镀膜法、 磁控溅射法、 电化学镀膜法或湿法涂覆法。  15. The method according to claim 8, wherein the physical coating method comprises a vacuum thermal plating method, a magnetron sputtering method, an electrochemical coating method or a wet coating method.
16、 如权利要求 8所述的方法， 其特征在于： 所述湿法涂覆法包括旋 涂、 喷涂、 丝印、 滴涂、 浸涂等印刷方法。  16. The method of claim 8, wherein: the wet coating method comprises a printing method such as spin coating, spray coating, silk screen printing, drop coating, dip coating, or the like.
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