WO2015085921A1 - Method for manufacturing thin-film solar cell semi-finished product - Google Patents

Method for manufacturing thin-film solar cell semi-finished product Download PDF

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Publication number
WO2015085921A1
WO2015085921A1 PCT/CN2014/093442 CN2014093442W WO2015085921A1 WO 2015085921 A1 WO2015085921 A1 WO 2015085921A1 CN 2014093442 W CN2014093442 W CN 2014093442W WO 2015085921 A1 WO2015085921 A1 WO 2015085921A1
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Prior art keywords
contact layer
front contact
layer
substrate
flame
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PCT/CN2014/093442
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French (fr)
Chinese (zh)
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德罗斯特克里斯蒂案
彭寿
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中国建材国际工程集团有限公司
Ctf 太阳能有限公司
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Publication of WO2015085921A1 publication Critical patent/WO2015085921A1/en

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    • 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
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/073—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar 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
    • 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
    • Y02E10/543—Solar cells from Group II-VI materials
    • 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 subject of the invention is an improved method for producing thin-film solar cells or semi-finished products for thin-film solar cells, wherein the method is provided to clean the front contact layer before subsequent application of other layers.
  • a transparent front contact layer (preferably a TCO-transparent conductive oxide) is applied to a substrate, typically glass.
  • a window layer-layer preferably composed of pure or modified CdS (cadmium sulfide), is deposited on the front contact layer, and a preferred CdTe layer (cadmium telluride) is deposited on the window layer The absorption layer.
  • CdS cadmium sulfide
  • CdTe layer cadmium telluride
  • CdS layer or the CdTe layer is carried out according to a method from the prior art.
  • a CSS (close spaced sublimation) method is often used in which a glass substrate with a TCO-front contact layer prepared in advance is moved over a crucible with CdS. The crucible is heated and the material to be vaporized (CdS) is evaporated (sublimed) by helium and precipitated on the front contact layer of the substrate, which is maintained at a lower temperature than helium.
  • Subsequent CdTe layer application is also preferably carried out in a CSS process.
  • a back contact preferably as a layer sequence, is applied.
  • tempering and closing steps are premised on the basis of the prior art and are not described in detail.
  • the same premise is that An anti-reflective layer and a protective layer (such as a backside laminate or a backside glass) are added.
  • the application of the window layer and the absorbing layer is generally carried out in such a way that the substrate with the pre-prepared front contact layer (which preferably points in the ⁇ direction) is heated and guided over the crucible at a constant speed. After that, a uniform thickness of the CdS and CdTe layers is formed.
  • the process is carried out in a heated vacuum chamber which is connected to one another in succession according to the prior art, the substrate being supported by the vacuum chamber on a transport system consisting of rollers or conveyors, wherein the rollers are supported. Or the conveyor belt supports the substrate on its side edges.
  • the window layer is designed to be as thin as possible in order to limit the deterioration of the optical properties of the solar cells that occur by absorption of light in such layers.
  • the window layer (often the CdS layer) does not have defect points (hole-pinholes) through which a short circuit can occur between the front contact and the next absorption layer (often the CdTe layer).
  • a CdS layer thickness of 60 nm to 200 nm is preferable in the case of a CdS window layer.
  • the current contact layer (preferably the TCO layer) may be disadvantageous when it has impurities. This can lead to defects in the front contact layer or in the layer (especially the window layer) situated thereon.
  • This type of uncleanness is often an organic substance such as a grease residue or a plastic residue, such as a plasticizer from a prefabricated packaging material of a glass substrate with a TCO layer.
  • DE 10 2010 006 681 A1 describes a method in which a TCO layer deposited before the application of the mirror layer and the substrate layer is in the case of a tandem solar cell in the case of a substrate structure. Deep cleaning is performed before the mirror layer is deposited. In this way, it should be possible to improve the adhesion of the mirror layer and it should be possible to deposit even without an adhesion layer. Cleaning is performed by an ion-supporting method. Described is a plasma cleaning method by rare gas or O 2 or N-containing gas. Also listed are ion sputtering or ion etching. But this additional cleaning process is expensive on the equipment.
  • DE 194 16 446 A1 describes an arrangement for cleaning a TCO-coated substrate for the production of amorphous silicon-based solar cells.
  • the same method used is the plasma method.
  • This plasma method is based on the use of CO 2 and is provided with special energy control during the cleaning and subsequent deposition processes.
  • a method for cleaning the surface of a glass substrate coated with TCO is proposed in WO 2010/120902 A2.
  • the proposed task is in particular to remove metal ions on the TCO layer.
  • the TCO layer is etched and contained in two processes of rinsing with deionized water.
  • An organic acid is used as an etchant.
  • WO 2012/089611 A2 setting flame cleaning The surface of the paper or carton to improve the adhesion of the surface.
  • the topmost substrate layer is oxidized.
  • US 2010/0162761 A1 describes a method for flame cleaning, in particular the surface of a glass body of flat glass.
  • Flat glass substrates used in LCD or plasma panel production must meet extremely high surface roughness requirements. In order to avoid complex surface polishing processes that are subject to high losses, it is recommended to flame clean the surface. This achieves to some extent the melting of the topmost glass layer and the smoothness of the roughness.
  • the proposed task is solved by a method according to claim 1.
  • Preferred methods are set forth in the dependent claims to which they are cited.
  • the method according to the invention is provided for flame cleaning of a TCO-front contact layer or a TCO-front contact layer sequence of a thin-film solar cell.
  • the main object of the method according to the invention is to remove surface organic impurities. This is achieved by treating the surface with a gas flame.
  • the aim in this case is to not heat the surface to the softening temperature or even the melting temperature of the TCO or the substrate (preferably float glass) arranged thereunder. This is guaranteed by processing only for a short period of time.
  • the surface temperature of the TCO surface of the substrate is preferably in the range from about 80 ° C to 220 ° C after the flame cleaning (initial temperature: 20 ° C), particularly preferably in the range from 80 ° C to 150 ° C, very particularly preferred.
  • the ground is in the range of 90 ° C to 120 ° C.
  • the temperature of the surface of the front contact layer is increased by flame cleaning preferably by a maximum of 200 K (Kelvin).
  • K Kelvin
  • the temperature rise is in the range of 60 ° C to 130 ° C, particularly preferably in the range of 70 ° C to 100 ° C. In any case, the temperature remains below the softening temperature of the TCO-layer or substrate.
  • the TCO coated surface of the substrate is flame cleaned by one or more gas flames.
  • the duration of the action of the flame on the surface is preferably between 1 s and 60 s, particularly preferably between 2 s and 30 s and very particularly preferably between 3 s and 10 s. Excellent results were obtained by flame cleaning for about 5 s.
  • the flame cleaning is directly followed by application of the front contact layer (for example by sputtering) or conventional wet chemical cleaning.
  • the CdS layer is applied to the flame-cleaned front contact layer immediately after the flame cleaning. It is further preferred that the adhesion-promoting layer for the CdS layer is deposited onto the flame-cleaned front contact layer immediately after the flame cleaning.
  • the gas flame is preferably produced by combustion of a commercially common fuel gas such as propane or butane or preferably a propane/butane mixture (80%/20%).
  • the combustion control is designed to keep the blue flame stable. This is achieved by a method according to the prior art, in particular by nozzle design and air coefficient control.
  • the carbon black particles or unburned hydrocarbons are specifically prevented from being deposited on the flame-cleaned surface by a blue flame (premixed flame).
  • the temperature in the region of the flame tip is preferably from about 900 °C to 1000 °C.
  • the TCO surface of the substrate has no pre-existing impurities. It is specifically determined that the surface is much infiltrated by water much better than it was before treatment. In addition to this, the adhesion of the layer applied to the treated TCO surface of the substrate is significantly improved. Obviously, activation of the TCO surface is achieved.
  • the additional clean flame cleaning according to the present invention is Particularly suitable.
  • the impurities are formed on the TCO glass during storage, and the method according to the invention can advantageously help to remove these impurities.
  • Flame cleaning advantageously complements conventional wet chemical cleaning (glass cleaning) of TCO coated substrates prior to CdS coating.
  • the method according to the invention can be integrated very well into the industrial production of thin-film solar cells.
  • a transport system eg, a roller transport system
  • the TCO layer is moved into the combustion chamber by means of a transport system (eg, a roller transport system) present in the unit and continuously Pass through the combustion chamber.
  • a transport system eg, a roller transport system
  • the TCO layer is pointing downwards, then one or more columns of gas are arranged perpendicular to the direction of motion. They extend over the overall width of the substrate and flame-clean the substrate from below.
  • the substrate is moved by the transport system and transported to the process steps for depositing the window layer, for example into a vacuum chamber for CSS deposition of the CdS layer, and subsequently introduced into the CdTe layer.
  • This flame removal from below is advantageous when, for example, in the case of the CSS method, the deposition of the window layer and the absorbing layer is also carried out from below. It is further advantageous that the substrate does not need to be twisted after flame cleaning prior to introduction into the vacuum chamber for CSS deposition. However, it is also possible to perform a flame cleaning of the TCO layer from above. This also has the advantage that the possible combustion residues are carried by the rising heat and are carried away from the TCO surface of the substrate. Obviously, the method can also be carried out in the case of a stationary substrate and a burner which is moved or only briefly opened.
  • the flame cleaning of the TCO layer of the substrate After the flame cleaning of the TCO layer of the substrate, it can be further processed by a method according to the prior art until a finished solar cell is realized.
  • the CdTe layer and the back contact layer sequence can be applied according to known methods. Variations and additional layers above the layer made of pure or modified CdS are also possible and are not affected by the use of the method according to the invention. In contrast, studies have shown that the adhesion of the CdS layer on the front contact layer is significantly improved.
  • the substrate having a size of 1600 mm ⁇ 200 mm ⁇ 3.2 mm was coated with a layer having a thickness of 250 nm made of indium tin oxide (ITO) as a transparent front contact layer.
  • ITO indium tin oxide
  • the substrate with the downwardly facing front contact layer is conveyed to the combustion chamber on a roller conveyor.
  • the substrate is moved at a continuous speed of 1.5 m/min and passes through a column of gas flames in the middle of the combustion chamber which extend across the entire width of the substrate and perpendicular to the direction of motion.
  • a mixture of propane and butane in a ratio of 80:20 is burned in a gas flame.
  • Combustion control ensures that the flame color remains blue and does not produce carbon black particles or the like.
  • the substrate entered the combustion chamber at a surface temperature of 21 °C.
  • the substrate is exposed to a gas flame for about 5 s in the interior of the combustion chamber.
  • the surface temperature after the flame cleaning was 105 °C.
  • the substrate is delivered to a subsequent processing chamber.
  • the CdS layer is now applied by the CSS method. ⁇
  • the thickness of the CdS layer obtained was 60 nm.
  • a CdTe layer having a thickness of 5000 nm was applied by a CSS method.
  • the application of the back contact layer(s) is carried out in a method according to the prior art.
  • the back contact layer consists of a layer sequence of the conditioning layer and the actual contact layer.
  • the conditioning layer was formed of Te (50 nm) by NP (nitrophosphate) etching of the CdTe layer, and a Mo layer (250 nm) as an actual contact layer was subsequently deposited on the conditioning layer.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
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Abstract

Provided is a method for manufacturing a thin-film solar cell semi-finished product, the method comprising the following steps: providing a transparent substrate having a front contact layer or a front contact layer sequence; and conducting flame scarfing on the front contact layer or the front contact layer sequence, the flame scarfing being conducted via one or more gas burners, and the surface temperature of the front contact layer being always maintained lower than the softening temperature of the front contact layer or the front contact layer sequence and the substrate. Provided is a method for cleaning the surface of a glass substrate coated with TCO. As a supplement to a traditional cleaning process, the method is easy to be integrated with well-known manufacturing processes and ensures a stable cleaning effect.

Description

用来制造用于薄层太阳能电池的半成品的方法Method for manufacturing a semi-finished product for a thin-film solar cell 技术领域Technical field
本发明的主题是用来制造薄层太阳能电池或用于薄层太阳能电池的半成品的改进的方法，其中，方法设置为，在后续地施加其他层之前清洁前接触层。The subject of the invention is an improved method for producing thin-film solar cells or semi-finished products for thin-film solar cells, wherein the method is provided to clean the front contact layer before subsequent application of other layers.
背景技术Background technique
在根据现有技术以基材上置结构的方式制造薄层太阳能电池时，在通常是玻璃的基材上施加透明的前接触层(优选TCO-透明导电氧化物(transparent conductive oxide))。在这种前接触层上沉积有优选由纯的或改性的CdS(硫化镉)构成的窗口层(Window Layer)-层，在该窗口层-层上接着沉积有优选CdTe层(碲化镉)的吸收层。最后进行背接触层或背接触层序列的施加。In the production of a thin-film solar cell in the manner of a substrate superstructure according to the prior art, a transparent front contact layer (preferably a TCO-transparent conductive oxide) is applied to a substrate, typically glass. A window layer-layer, preferably composed of pure or modified CdS (cadmium sulfide), is deposited on the front contact layer, and a preferred CdTe layer (cadmium telluride) is deposited on the window layer The absorption layer. Finally, the application of the back contact layer or the back contact layer sequence is carried out.
CdS层或CdTe层的施加根据出自现有技术的方法进行。在这种情况下经常使用CSS(近空间升华(close spaced sublimation))方法，其中，带有预先准备的TCO-前接触层的玻璃基材在带有CdS的坩埚上方运动。该坩埚被加热并且待汽化渗镀的材料(CdS)由坩埚蒸发(升华)并且沉淀在基材的前接触层上，该前接触层被保持在比坩埚更低的温度下。The application of the CdS layer or the CdTe layer is carried out according to a method from the prior art. In this case, a CSS (close spaced sublimation) method is often used in which a glass substrate with a TCO-front contact layer prepared in advance is moved over a crucible with CdS. The crucible is heated and the material to be vaporized (CdS) is evaporated (sublimed) by helium and precipitated on the front contact layer of the substrate, which is maintained at a lower temperature than helium.
后续的CdTe层施加同样优选以CSS方法进行。Subsequent CdTe layer application is also preferably carried out in a CSS process.
最后，施加优选作为层序列的背接触。Finally, a back contact, preferably as a layer sequence, is applied.
在所描述的方法中以及在下文中，回火和封闭步骤根据现有技术作为公知地设为前提的并且不进行详细描述。同样设为前提的是，施 加抗反射层和防护层(例如背侧层叠物或背侧玻璃)。In the described method and in the following, the tempering and closing steps are premised on the basis of the prior art and are not described in detail. The same premise is that An anti-reflective layer and a protective layer (such as a backside laminate or a backside glass) are added.
在产业规模的使用中，窗口层和吸收层的施加通常以以下方式进行，即，带有预先准备的前接触层(其优选指向坩埚方向)的基材被加热并且以恒定速度在坩埚上方引导经过，从而形成均匀厚度的CdS和CdTe层。该过程根据现有技术在彼此相继地联接的、加热的真空室中实施，基材在由辊子或传送带构成的传输系统上、在传动体上受支承地运动通过这些真空室，其中，这些辊子或传送带在其侧棱边上支撑基材。In industrial scale use, the application of the window layer and the absorbing layer is generally carried out in such a way that the substrate with the pre-prepared front contact layer (which preferably points in the 坩埚 direction) is heated and guided over the crucible at a constant speed. After that, a uniform thickness of the CdS and CdTe layers is formed. The process is carried out in a heated vacuum chamber which is connected to one another in succession according to the prior art, the substrate being supported by the vacuum chamber on a transport system consisting of rollers or conveyors, wherein the rollers are supported. Or the conveyor belt supports the substrate on its side edges.
在这种过程中所追求的是，窗口层设计得尽可能薄，以便对通过在这种层中的光吸收而发生的太阳能电池的光学特性恶化加以限制。然而同时必须保障，窗口层(经常是CdS层)不具有缺陷点(孔-针孔)，通过缺陷点可能在前接触和紧接着的吸收层(经常是CdTe层)之间发生短路。根据现有技术，为了满足这两种需求，在CdS窗口层的情况下优选60nm到200nm的CdS层厚度。What is sought in this process is that the window layer is designed to be as thin as possible in order to limit the deterioration of the optical properties of the solar cells that occur by absorption of light in such layers. At the same time, however, it must be ensured that the window layer (often the CdS layer) does not have defect points (hole-pinholes) through which a short circuit can occur between the front contact and the next absorption layer (often the CdTe layer). According to the prior art, in order to satisfy these two requirements, a CdS layer thickness of 60 nm to 200 nm is preferable in the case of a CdS window layer.
在窗口层制造中，当前接触层(优选TCO层)具有不洁物时，可能是不利的。这可以在前接触层中或者位于其上的层(特别是窗口层)中导致缺陷。这种类型的不洁物经常是例如为油脂残留物或者塑料残留物的有机物质，例如出自预制的带有TCO层的玻璃基材的包装材料的增塑剂。In window layer fabrication, the current contact layer (preferably the TCO layer) may be disadvantageous when it has impurities. This can lead to defects in the front contact layer or in the layer (especially the window layer) situated thereon. This type of uncleanness is often an organic substance such as a grease residue or a plastic residue, such as a plasticizer from a prefabricated packaging material of a glass substrate with a TCO layer.
研究表明了，常规的清洗或冲洗过程是不适用于把在基材的TCO覆层上的有机不洁物充分地去除的。Studies have shown that conventional cleaning or rinsing processes are not suitable for adequate removal of organic impurities on the TCO coating of the substrate.
基材的表面不洁物问题是公知的并且在现有技术中以不同的方法解决。Surface imperfections of substrates are well known and are addressed in different ways in the prior art.
DE 10 2010 006 681 A1描述了一种方法，其中，在基材结构中的 串结太阳能电池的情况下，在此在施加镜面层(Spiegelschicht)和基材层的之前沉积下来的TCO层在接下来的镜面层沉积之前进行深度清洁。以这种方式，应当可以改进镜面层的粘附力并且应当可以甚至无需增附层地进行沉积。清洁通过离子支持性方法进行。所描述的是通过稀有气体或者O2或者含N气体的等离子清洁方法。此外还列出的是离子溅射或离子蚀刻。但是这种附加的清洁过程是在设备上昂贵的。DE 10 2010 006 681 A1 describes a method in which a TCO layer deposited before the application of the mirror layer and the substrate layer is in the case of a tandem solar cell in the case of a substrate structure. Deep cleaning is performed before the mirror layer is deposited. In this way, it should be possible to improve the adhesion of the mirror layer and it should be possible to deposit even without an adhesion layer. Cleaning is performed by an ion-supporting method. Described is a plasma cleaning method by rare gas or O 2 or N-containing gas. Also listed are ion sputtering or ion etching. But this additional cleaning process is expensive on the equipment.
DE 194 16 446 A1描述了一种设置，以便清洁用于制造基于非晶硅的太阳能电池的、以TCO覆层的基材。所使用的同样是等离子方法。该等离子方法基于使用CO2并且在清洁和随后的沉积过程期间设置有特殊的能量控制。DE 194 16 446 A1 describes an arrangement for cleaning a TCO-coated substrate for the production of amorphous silicon-based solar cells. The same method used is the plasma method. This plasma method is based on the use of CO 2 and is provided with special energy control during the cleaning and subsequent deposition processes.
在WO 2010/120902 A2中提出了一种用于清洁以TCO覆层的玻璃基材表面的方法。所提出的任务特别是去除在TCO层上的金属离子。为此设置了，对TCO层进行过蚀刻，其包含在两个以去离子水冲洗的过程中。作为蚀刻剂使用有机酸。A method for cleaning the surface of a glass substrate coated with TCO is proposed in WO 2010/120902 A2. The proposed task is in particular to remove metal ions on the TCO layer. For this purpose, the TCO layer is etched and contained in two processes of rinsing with deionized water. An organic acid is used as an etchant.
WO 2012/089611 A2设置，火焰清理
Figure PCTCN2014093442-appb-000001
纸或纸箱的表面，以便改进表面的附着力。在该方法中，最顶部的基材层被氧化。WO 2012/089611 A2 setting, flame cleaning
Figure PCTCN2014093442-appb-000001
The surface of the paper or carton to improve the adhesion of the surface. In this method, the topmost substrate layer is oxidized.
US 2010/0162761 A1描述了一种用于火焰清理特别是平板玻璃的玻璃体的表面的方法。用于LCD或等离子面板生产的平板玻璃基材必须在表面粗糙度方面满足极高的要求。为了回避复杂的并且要承担高损失的表面抛光过程，建议对表面进行火焰清理。这在某种程度上实现了熔融最顶部的玻璃层并且平整粗糙度。US 2010/0162761 A1 describes a method for flame cleaning, in particular the surface of a glass body of flat glass. Flat glass substrates used in LCD or plasma panel production must meet extremely high surface roughness requirements. In order to avoid complex surface polishing processes that are subject to high losses, it is recommended to flame clean the surface. This achieves to some extent the melting of the topmost glass layer and the smoothness of the roughness.
所描述的方法或者在设备和/或能量上耗费巨大，或者这些方法只能不良地整合在根据现有技术的太阳能电池生产的连续的贯通过程中。 The described methods are either costly in terms of equipment and/or energy, or they can only be poorly integrated in a continuous through process of solar cell production according to the prior art.
发明内容Summary of the invention
这导致提出了以下任务：提出一种针对玻璃基材的以TCO覆层的表面的清洁方法(也作为对传统的清洗过程的补充)，其易于整合到公知的制作工程中并且保障了稳定的清洁成效。This has led to the task of proposing a TCO-coated surface cleaning method for glass substrates (also as a complement to conventional cleaning processes), which is easy to integrate into known manufacturing processes and guarantees stability. Cleaning results.
根据本发明，所提出的任务通过根据权利要求1的方法解决。优选的方法在引用其的从属权利要求中提出。According to the invention, the proposed task is solved by a method according to claim 1. Preferred methods are set forth in the dependent claims to which they are cited.
根据本发明的方法设置为，对薄层太阳能电池的TCO-前接触层或TCO-前接触层序列进行火焰清理。The method according to the invention is provided for flame cleaning of a TCO-front contact layer or a TCO-front contact layer sequence of a thin-film solar cell.
根据本发明的方法的主要目的为，去除表面的有机不洁物。这通过以气体火焰处理表面的方式实现。在这种情况下目的在于，不把表面加热到TCO或布置在其下方的基材(优选浮法玻璃)的软化温度或者乃至熔融温度。这通过处理仅进行短时间来保障。研究表明，基材的TCO表面的表面温度在火焰清理之后优选在约80℃到220℃的范围中(初始温度：20℃)，特别优选地在80℃到150℃的范围中，十分特别优选地在90℃到120℃的范围中。为了消除在前接触层上附着的不洁物，根据本发明，前接触层(TCO层)表面的温度由于火焰清理导致升高了优选最大200K(开尔文)就是足够的。然而在需要时可行的是，只要前接触层和/或基材的温度保持低于软化温度，可以将前接触层的温度升高选择得更高。优选地，温度升高在60℃到130℃的范围中，特别优选在70℃到100℃的范围中。在任何情况下，温度保持低于(unterhalb)TCO-层或基材的软化温度。The main object of the method according to the invention is to remove surface organic impurities. This is achieved by treating the surface with a gas flame. The aim in this case is to not heat the surface to the softening temperature or even the melting temperature of the TCO or the substrate (preferably float glass) arranged thereunder. This is guaranteed by processing only for a short period of time. Studies have shown that the surface temperature of the TCO surface of the substrate is preferably in the range from about 80 ° C to 220 ° C after the flame cleaning (initial temperature: 20 ° C), particularly preferably in the range from 80 ° C to 150 ° C, very particularly preferred. The ground is in the range of 90 ° C to 120 ° C. In order to eliminate the impurities attached to the front contact layer, according to the invention, the temperature of the surface of the front contact layer (TCO layer) is increased by flame cleaning preferably by a maximum of 200 K (Kelvin). However, it is possible, if desired, to increase the temperature rise of the front contact layer as long as the temperature of the front contact layer and/or substrate remains below the softening temperature. Preferably, the temperature rise is in the range of 60 ° C to 130 ° C, particularly preferably in the range of 70 ° C to 100 ° C. In any case, the temperature remains below the softening temperature of the TCO-layer or substrate.
根据本发明，基材的经过TCO覆层的表面通过一个或多个气体火焰进行火焰清理。火焰作用到表面上的持续时间为优选在1s和60s之间，特别优选地在2s和30s之间并且十分特别优选地在3s和10s之间。通过持续约5s的火焰清理获得了优异的效果。 According to the invention, the TCO coated surface of the substrate is flame cleaned by one or more gas flames. The duration of the action of the flame on the surface is preferably between 1 s and 60 s, particularly preferably between 2 s and 30 s and very particularly preferably between 3 s and 10 s. Excellent results were obtained by flame cleaning for about 5 s.
在特别优选的实施方式中，火焰清理直接地紧随着(例如通过溅射进行的)前接触层的施加或者常规的湿法化学清洁。在其他优选的实施方式中，在火焰清理后紧接着把CdS层施加在经火焰清理的前接触层上。进一步优选的是，在火焰清理后紧接着把用于CdS层的增附层沉积到经火焰清理的前接触层上。In a particularly preferred embodiment, the flame cleaning is directly followed by application of the front contact layer (for example by sputtering) or conventional wet chemical cleaning. In other preferred embodiments, the CdS layer is applied to the flame-cleaned front contact layer immediately after the flame cleaning. It is further preferred that the adhesion-promoting layer for the CdS layer is deposited onto the flame-cleaned front contact layer immediately after the flame cleaning.
气体火焰优选通过商业上常见的燃料气体、例如丙烷或丁烷或者优选丙烷/丁烷混合物(80％/20％)的燃烧产生。燃烧控制设计为：使蓝色火焰维持稳定。这通过根据现有技术的方法实现，特别是通过喷嘴设计和空气系数控制实现。通过蓝色火焰(预混火焰)特别地避免了炭黑颗粒或未燃尽的烃类沉淀在已火焰清理的表面上。在火焰尖端的区域中的温度优选为约900℃到1000℃。The gas flame is preferably produced by combustion of a commercially common fuel gas such as propane or butane or preferably a propane/butane mixture (80%/20%). The combustion control is designed to keep the blue flame stable. This is achieved by a method according to the prior art, in particular by nozzle design and air coefficient control. The carbon black particles or unburned hydrocarbons are specifically prevented from being deposited on the flame-cleaned surface by a blue flame (premixed flame). The temperature in the region of the flame tip is preferably from about 900 °C to 1000 °C.
在根据本发明的火焰清理的结果中观察到的是，基材的TCO表面没有之前存在的不洁物。特别确定的是，表面比在处理之前的情况好得多地被水浸润。除此之外，明显地改善了施加到基材的经处理的TCO表面上的层的粘附力。显然，实现了TCO表面的活化。It is observed in the results of the flame cleaning according to the invention that the TCO surface of the substrate has no pre-existing impurities. It is specifically determined that the surface is much infiltrated by water much better than it was before treatment. In addition to this, the adhesion of the layer applied to the treated TCO surface of the substrate is significantly improved. Obviously, activation of the TCO surface is achieved.
当以TCO覆层的玻璃(基材)产业规模地制作并提供时并且在第一次清洗及覆层之前或多或少地长时间储存时，则根据本发明作为附加的清洁的火焰清理是特别适用的。在储存期间在TCO玻璃上构成不洁物，根据本发明的方法可以有利地有助于清除这些不洁物。火焰清理有利地补充了在以CdS覆层之前的、以TCO覆层的基材的常规湿法化学清洁(玻璃清洗)。When the TCO coated glass (substrate) is produced and supplied on an industrial scale and is stored more or less for a long time before the first cleaning and coating, then the additional clean flame cleaning according to the present invention is Particularly suitable. The impurities are formed on the TCO glass during storage, and the method according to the invention can advantageously help to remove these impurities. Flame cleaning advantageously complements conventional wet chemical cleaning (glass cleaning) of TCO coated substrates prior to CdS coating.
根据本发明的方法可以非常良好地整合到薄层太阳能电池的工业化生产中。在把TCO层施加到平的玻璃基材上之后(或提供预制的TCO/基材半成品之后)，其借助于在机组中存在的传输系统(例如辊子传输系统)运动到燃烧室中并且连续地穿过该燃烧室。如果此外例如TCO层指向向下，那么垂直于运动方向布置有一列或多列气体燃烧 器，它们延伸过基材的整体宽度并且从下方出发地对基材进行火焰清理。随后，基材被传输系统继续移动并且被输送给用于沉积窗口层的过程步骤、(例如输送到用于CdS层的CSS沉积的真空室中)，并且随后引入CdTe层。当例如在CSS方法的情况下窗口层和吸收层的沉积也从下方进行时，那么这种从下方的火焰清理是有利的。此外有利的是，因此在为进行CSS沉积而引入真空室之前，无需在火焰清理后扭转基材。然而同样可行的是，从上方出发对TCO层进行火焰清理。这还具有如下优点，即，使可能的燃烧残余物通过向上升的热所携带，并且从基材的TCO表面被带走。显而易见地，该方法也可以在静止的基材和运动的或者仅短暂地打开的燃烧器的情况下进行。The method according to the invention can be integrated very well into the industrial production of thin-film solar cells. After applying the TCO layer to a flat glass substrate (or after providing a prefabricated TCO/substrate semi-finished product), it is moved into the combustion chamber by means of a transport system (eg, a roller transport system) present in the unit and continuously Pass through the combustion chamber. If, for example, the TCO layer is pointing downwards, then one or more columns of gas are arranged perpendicular to the direction of motion. They extend over the overall width of the substrate and flame-clean the substrate from below. Subsequently, the substrate is moved by the transport system and transported to the process steps for depositing the window layer, for example into a vacuum chamber for CSS deposition of the CdS layer, and subsequently introduced into the CdTe layer. This flame removal from below is advantageous when, for example, in the case of the CSS method, the deposition of the window layer and the absorbing layer is also carried out from below. It is further advantageous that the substrate does not need to be twisted after flame cleaning prior to introduction into the vacuum chamber for CSS deposition. However, it is also possible to perform a flame cleaning of the TCO layer from above. This also has the advantage that the possible combustion residues are carried by the rising heat and are carried away from the TCO surface of the substrate. Obviously, the method can also be carried out in the case of a stationary substrate and a burner which is moved or only briefly opened.
在基材的TCO层的火焰清理之后，可以通过根据现有技术的方法进一步加工直至实现成品太阳能电池。因此例如可以根据公知方法施加CdTe层和背接触层序列。变型方案和在由纯的或改性的CdS的制成的层的上方的附加层也是可行的，并且不通过根据本发明的方法的使用而受影响。相反，研究表明，CdS层在前接触层上的粘附力是显著地改善的。After the flame cleaning of the TCO layer of the substrate, it can be further processed by a method according to the prior art until a finished solar cell is realized. Thus, for example, the CdTe layer and the back contact layer sequence can be applied according to known methods. Variations and additional layers above the layer made of pure or modified CdS are also possible and are not affected by the use of the method according to the invention. In contrast, studies have shown that the adhesion of the CdS layer on the front contact layer is significantly improved.
具体实施方式detailed description
具有1600mm×200mm×3.2mm尺寸的基材通过作为透明的前接触层的、由氧化铟锡(ITO)制成的厚度为250nm的层加以覆层。The substrate having a size of 1600 mm × 200 mm × 3.2 mm was coated with a layer having a thickness of 250 nm made of indium tin oxide (ITO) as a transparent front contact layer.
随后，带有指向向下的前接触层的基材在辊子传输设备上被输送到燃烧室中。基材以1.5m/min的连续速度运动，并且在燃烧室的中部穿过一列气体火焰，这些气体火焰越过基材的整个宽度并且垂直于运动方向延伸。以80:20比例的丙烷和丁烷制成的混合物在气体火焰中燃烧。燃烧控制保障了火焰颜色保持蓝色并且不生成炭黑颗粒或类似物。基材以21℃的表面温度进入燃烧室。基材在燃烧室内部中暴露在气体火焰下约5s。在火焰清理后表面温度为105℃。在火焰清理后，基材被输送到后续的处理室中。在此，现在以CSS方法施加CdS层。所达 到的CdS层厚度为60nm。随后，以CSS方法施加具有5000nm厚度的CdTe层。之后，以根据现有技术的方法进行(一个或多个)背接触层的施加。在此，背接触层由调节层和实际的接触层的层序列组成。在此，调节层通过对CdTe层的NP(硝磷酸)蚀刻由Te(50nm)形成，在调节层上接着沉积作为实际的接触层的Mo层(250nm)。Subsequently, the substrate with the downwardly facing front contact layer is conveyed to the combustion chamber on a roller conveyor. The substrate is moved at a continuous speed of 1.5 m/min and passes through a column of gas flames in the middle of the combustion chamber which extend across the entire width of the substrate and perpendicular to the direction of motion. A mixture of propane and butane in a ratio of 80:20 is burned in a gas flame. Combustion control ensures that the flame color remains blue and does not produce carbon black particles or the like. The substrate entered the combustion chamber at a surface temperature of 21 °C. The substrate is exposed to a gas flame for about 5 s in the interior of the combustion chamber. The surface temperature after the flame cleaning was 105 °C. After the flame is cleaned, the substrate is delivered to a subsequent processing chamber. Here, the CdS layer is now applied by the CSS method.达达 The thickness of the CdS layer obtained was 60 nm. Subsequently, a CdTe layer having a thickness of 5000 nm was applied by a CSS method. Thereafter, the application of the back contact layer(s) is carried out in a method according to the prior art. In this case, the back contact layer consists of a layer sequence of the conditioning layer and the actual contact layer. Here, the conditioning layer was formed of Te (50 nm) by NP (nitrophosphate) etching of the CdTe layer, and a Mo layer (250 nm) as an actual contact layer was subsequently deposited on the conditioning layer.
最后，根据现有技术进行其他的加工步骤。 Finally, other processing steps are carried out in accordance with the prior art.

Claims (6)

  1. 一种用来制造用于薄层太阳能电池的半成品的方法，所述方法包括以下步骤：A method for manufacturing a semi-finished product for a thin-film solar cell, the method comprising the steps of:
    a.提供带有前接触层或前接触层序列的透明基材；a. providing a transparent substrate with a front contact layer or a front contact layer sequence;
    b.对所述前接触层或前接触层序列进行火焰清理，b. performing flame cleaning on the front contact layer or the front contact layer sequence,
    其特征在于，所述火焰清理通过一个或多个气体燃烧器进行，其中，所述前接触层的表面温度始终保持低于所述前接触层或前接触层序列和基材的软化温度。Characterized in that the flame cleaning is performed by one or more gas burners, wherein the surface temperature of the front contact layer is always kept below the softening temperature of the front contact layer or front contact layer sequence and the substrate.
  2. 根据权利要求1所述的方法，其特征在于，通过所述火焰清理导致的所述前接触层或前接触层序列的表面温度升高为最大200开尔文。The method of claim 1 wherein the surface temperature of said front contact layer or front contact layer sequence caused by said flame cleaning is increased to a maximum of 200 Kelvin.
  3. 根据权利要求1或2所述的方法，其特征在于，在施加透明导电氧化物前接触层或前接触层序列之后紧接着进行所述火焰清理。Method according to claim 1 or 2, characterized in that the flame cleaning is carried out immediately after the application of the transparent conductive oxide front contact layer or the front contact layer sequence.
  4. 根据权利要求1或2所述的方法，其特征在于，在所述火焰清理之后紧接着进行后续的窗口层涂覆。Method according to claim 1 or 2, characterized in that subsequent window layer coating is carried out immediately after the flame cleaning.
  5. 根据以上所述权利要求中任意一项所述的方法，其特征在于，所述火焰清理通过一个或多个气体燃烧器进行，所述气体燃烧器以蓝色预混火焰工作。A method according to any of the preceding claims, wherein the flame cleaning is performed by one or more gas burners that operate in a blue premixed flame.
  6. 根据以上所述权利要求中任意一项所述的方法，其特征在于，所述基材连续地输送穿过燃烧室，在所述燃烧室中进行所述火焰清理。 A method according to any of the preceding claims, wherein the substrate is continuously conveyed through a combustion chamber in which the flame cleaning is performed.
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