CN110061094A - Cadmium telluride thin film battery surface cleaning pretreatment process - Google Patents
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- 239000010409 thin film Substances 0.000 title abstract description 51
- 238000004140 cleaning Methods 0.000 title abstract description 33
- 238000000034 method Methods 0.000 title abstract description 33
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000000758 substrate Substances 0.000 abstract description 47
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 abstract description 42
- 239000000243 solution Substances 0.000 abstract description 20
- 239000010408 film Substances 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000001590 oxidative effect Effects 0.000 abstract description 11
- 239000007800 oxidant agent Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F71/00—Manufacture or treatment of devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/10—Semiconductor bodies
- H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
- H10F77/169—Thin semiconductor films on metallic or insulating substrates
- H10F77/1696—Thin semiconductor films on metallic or insulating substrates the films including Group II-VI materials, e.g. CdTe or CdS
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- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
本发明公开了一种碲化镉薄膜电池表面清洗预处理工艺，其包括以下步骤：使用含氧化剂的第一清洗液清洗薄膜基板；使用纯水清洗薄膜基板；干燥薄膜基板以除去薄膜基板表面的液体；在薄膜基板表面添加氯化镉水溶液。第一清洗液具有一定的氧化作用，使得碲化镉层表面更亲水，同时也可起到清洁碲化镉层表面的作用，通过此方法清洗过的膜面，表面添加的氯化镉水溶液分布得更均匀，氯化镉的结晶聚合更细，高温处理后外观上不会留下暗斑，由此可改善碲化镉薄膜电池膜面外观以及提升电池转换效率。
The present invention discloses a surface cleaning pretreatment process for a cadmium telluride thin film battery, which comprises the following steps: using a first cleaning solution containing an oxidant to clean a thin film substrate; using pure water to clean the thin film substrate; drying the thin film substrate to remove the liquid on the surface of the thin film substrate; and adding a cadmium chloride aqueous solution to the surface of the thin film substrate. The first cleaning solution has a certain oxidizing effect, making the surface of the cadmium telluride layer more hydrophilic, and can also play a role in cleaning the surface of the cadmium telluride layer. The cadmium chloride aqueous solution added to the surface of the film surface cleaned by this method is more evenly distributed, the crystal aggregation of cadmium chloride is finer, and no dark spots are left on the appearance after high temperature treatment, thereby improving the appearance of the cadmium telluride thin film battery film surface and improving the battery conversion efficiency.
Description
技术领域technical field
本发明涉及碲化镉薄膜电池生产技术领域，特别是碲化镉薄膜电池表面清洗预处理工艺。The invention relates to the technical field of cadmium telluride thin film battery production, in particular to a surface cleaning and pretreatment process of the cadmium telluride thin film battery.
背景技术Background technique
现有的工艺流程，要获得更高效的碲化镉薄膜太阳能电池，需要对薄膜基板使用氯化镉溶液处理后高温活化，而在用氯化镉溶液处理时，薄膜表面的氯化镉重结晶较为严重，高温活化后，有结晶的区域会在膜面留下暗斑，氯化镉溶液在膜面分布不均匀的地方会留下水纹印记。高温活化后这些印记很难清洗掉，这样对产品的外观有影响，同时氯化镉在表面分布的均匀性也会影响电池转换效率。为改善产品外观，提高电池转换效率，有必要改进碲化镉膜面清洗预处理技术，用以改善膜面外观及提升电池转换效率。In the existing technological process, in order to obtain a more efficient cadmium telluride thin film solar cell, the thin film substrate needs to be treated with a cadmium chloride solution and then activated at a high temperature. More serious, after high temperature activation, the crystalline area will leave dark spots on the film surface, and the cadmium chloride solution will leave water marks on the uneven distribution of the film surface. These marks are difficult to clean after high temperature activation, which affects the appearance of the product, and the uniformity of the distribution of cadmium chloride on the surface will also affect the cell conversion efficiency. In order to improve product appearance and improve cell conversion efficiency, it is necessary to improve the cadmium telluride film surface cleaning and pretreatment technology to improve the film surface appearance and improve cell conversion efficiency.
发明内容SUMMARY OF THE INVENTION
本发明提供一种碲化镉薄膜电池表面清洗预处理工艺，用以改善碲化镉薄膜电池膜面外观以及提升电池转换效率。The invention provides a surface cleaning and pretreatment process of a cadmium telluride thin film battery, which is used to improve the appearance of the film surface of the cadmium telluride thin film battery and improve the conversion efficiency of the battery.
本发明解决其技术问题所采用的技术方案是：The technical scheme adopted by the present invention to solve its technical problems is:
一种碲化镉薄膜电池表面清洗预处理工艺，用于处理薄膜基板，所述薄膜基板的表面具有碲化镉膜层，所述清洗预处理工艺包括以下步骤：A cadmium telluride thin film battery surface cleaning pretreatment process is used for processing a thin film substrate, the surface of the thin film substrate has a cadmium telluride film layer, and the cleaning pretreatment process includes the following steps:
步骤1，使用含氧化剂的第一清洗液清洗薄膜基板；Step 1, using a first cleaning solution containing an oxidant to clean the thin film substrate;
步骤2，使用纯水清洗薄膜基板；Step 2, using pure water to clean the thin film substrate;
步骤3，干燥薄膜基板以除去薄膜基板表面的液体；Step 3, drying the thin film substrate to remove the liquid on the surface of the thin film substrate;
步骤4，在薄膜基板表面添加氯化镉水溶液。Step 4, adding a cadmium chloride aqueous solution on the surface of the thin film substrate.
优选的，所述氧化剂为H2O2或者O3。Preferably, the oxidant is H 2 O 2 or O 3 .
优选的，所述第一清洗液中，H2O2的质量浓度为0.25％～10％，余量为水。Preferably, in the first cleaning solution, the mass concentration of H 2 O 2 is 0.25% to 10%, and the balance is water.
优选的，步骤1中，通过冲洗法清洗薄膜基板,冲洗时间为5～60S,第一清洗液的温度为20～45℃。Preferably, in step 1, the thin film substrate is cleaned by a rinsing method, the rinsing time is 5-60S, and the temperature of the first cleaning solution is 20-45°C.
优选的，步骤2中，通过冲洗法清洗薄膜基板。Preferably, in step 2, the thin film substrate is cleaned by a rinsing method.
优选的，步骤3中，通过烘干法或热风吹干法干燥薄膜基板。Preferably, in step 3, the film substrate is dried by a drying method or a hot air drying method.
优选的，步骤4中，通过喷涂法或者辊涂法或者浸泡法在薄膜基板表面添加氯化镉水溶液。Preferably, in step 4, an aqueous solution of cadmium chloride is added to the surface of the thin film substrate by spraying method, roller coating method or soaking method.
优选的，步骤4中，氯化镉水溶液中，氯化镉的质量浓度为13％～20％。Preferably, in step 4, in the cadmium chloride aqueous solution, the mass concentration of cadmium chloride is 13%-20%.
本发明的有益效果是：本发明中，使用含氧化剂的第一清洗液清洗薄膜基板，第一清洗液具有一定的氧化作用，使得碲化镉层表面更亲水，同时也可起到清洁碲化镉层表面的作用，通过此方法清洗过的膜面，表面添加的氯化镉水溶液分布得更均匀，氯化镉的结晶聚合更细，高温处理后外观上不会留下暗斑，由此可改善碲化镉薄膜电池膜面外观以及提升电池转换效率。The beneficial effects of the present invention are: in the present invention, the first cleaning solution containing an oxidant is used to clean the thin film substrate, and the first cleaning solution has a certain oxidation effect, making the surface of the cadmium telluride layer more hydrophilic, and at the same time, it can also clean the tellurium The role of the surface of the cadmium chloride layer, the film surface cleaned by this method, the cadmium chloride aqueous solution added to the surface is more evenly distributed, the crystal polymerization of cadmium chloride is finer, and there will be no dark spots on the appearance after high temperature treatment. This can improve the appearance of the film surface of the cadmium telluride thin film battery and improve the conversion efficiency of the battery.
附图说明Description of drawings
下面结合附图和实施例对本发明进一步说明：Below in conjunction with accompanying drawing and embodiment, the present invention is further described:
图1是本发明的工艺流程图。Fig. 1 is a process flow diagram of the present invention.
具体实施方式Detailed ways
参照图1，一种碲化镉薄膜电池表面清洗预处理工艺，用于处理薄膜基板，该薄膜基板的表面具有碲化镉膜层，该清洗预处理工艺包括以下步骤：Referring to FIG. 1, a surface cleaning and pretreatment process of a cadmium telluride thin film battery is used for processing a thin film substrate, and the surface of the thin film substrate has a cadmium telluride film layer, and the cleaning pretreatment process includes the following steps:
步骤1，使用含氧化剂的第一清洗液清洗薄膜基板；Step 1, using a first cleaning solution containing an oxidant to clean the thin film substrate;
步骤2，使用纯水清洗薄膜基板；Step 2, using pure water to clean the thin film substrate;
步骤3，干燥薄膜基板以除去薄膜基板表面的液体；Step 3, drying the thin film substrate to remove the liquid on the surface of the thin film substrate;
步骤4，在薄膜基板表面添加氯化镉水溶液。Step 4, adding a cadmium chloride aqueous solution on the surface of the thin film substrate.
经过上述步骤，即可完成碲化镉薄膜电池表面清洗预处理，以便进行下一步的高温活化。After the above steps, the surface cleaning and pretreatment of the cadmium telluride thin film battery can be completed, so as to perform the next step of high temperature activation.
本发明中，氧化剂为H2O2，且H2O2的质量浓度为0.25％～10％，第一清洗液的余量为水。优选的，H2O2的质量浓度为0.9％～1.5％。含H2O2的第一清洗液可对碲化镉层具有一定的氧化性，使得碲化镉层表面更亲水，同时也可起到清洁碲化镉层表面的作用。H2O2的分解残留物为水，不会导致薄膜基板受到污染。此外，氧化剂亦可采用O3，其中，O3的含量为2～20mg/L。In the present invention, the oxidant is H 2 O 2 , and the mass concentration of H 2 O 2 is 0.25% to 10%, and the balance of the first cleaning solution is water. Preferably, the mass concentration of H 2 O 2 is 0.9% to 1.5%. The first cleaning solution containing H 2 O 2 can have a certain oxidizing property on the cadmium telluride layer, so that the surface of the cadmium telluride layer is more hydrophilic, and can also play a role in cleaning the surface of the cadmium telluride layer. The decomposition residue of H2O2 is water, which does not cause contamination of the thin film substrate. In addition, O 3 can also be used as the oxidant, wherein the content of O 3 is 2-20 mg/L.
具体的，步骤1中，通过浸泡法或冲洗法清洗薄膜基板。浸泡法即将薄膜基板放入盛放有第一清洗液的第一容器中进行一段时间的浸泡，冲洗法则是通过喷头等装置将第一清洗液喷洒在薄膜基板上。Specifically, in step 1, the thin film substrate is cleaned by a soaking method or a rinsing method. The immersion method involves placing the thin film substrate in a first container containing the first cleaning solution for a period of time. The rinsing method is to spray the first cleaning solution on the thin film substrate through a nozzle or other device.
当通过冲洗法清洗薄膜基板，冲洗时间为5～60S，第一清洗液的温度为20～45℃，当水温较高时，可相应缩短冲洗时间。例如，可选择第一清洗液的温度为35～40℃，冲洗时间为25～60S。通过浸泡法清洗薄膜基板时，浸泡时间为5～60S，第一清洗液的温度为20～45℃。为优化清洗效果，可将薄膜基板多次提出液面，亦可驱动薄膜基板在第一清洗液内移动或转动。在完成薄膜基板的清洗后，使用检测装置检测第一容器内的液体中所含氧化剂的浓度，当低于预设值时将添加更高浓度的第一清洗液。When the thin film substrate is cleaned by the rinsing method, the rinsing time is 5-60S, and the temperature of the first cleaning solution is 20-45°C. When the water temperature is high, the rinsing time can be shortened accordingly. For example, the temperature of the first cleaning solution can be selected to be 35-40° C., and the rinsing time can be selected to be 25-60 s. When cleaning the thin film substrate by the soaking method, the soaking time is 5-60S, and the temperature of the first cleaning solution is 20-45°C. In order to optimize the cleaning effect, the thin film substrate can be lifted out of the liquid surface for many times, and the thin film substrate can also be driven to move or rotate in the first cleaning solution. After the cleaning of the thin film substrate is completed, a detection device is used to detect the concentration of the oxidant contained in the liquid in the first container, and a higher concentration of the first cleaning solution will be added when the concentration is lower than the preset value.
在步骤2中，亦可通过冲洗法或超声波清洗法清洗薄膜基板。冲洗时间为10～60S，依据水量的大小来调整时间，水量较大时可冲洗较短的时间，反之冲洗较长的时间。超声波清洗法即将薄膜基板置于盛放有纯水的第二容器，通过设置超声波装置来对薄膜基板进行震荡清洗。在完成薄膜基板的清洗后，使用检测装置检测第二容器内的液体中所含氧化剂的浓度，当超出预设值时将纯水更换。In step 2, the thin film substrate may also be cleaned by a rinsing method or an ultrasonic cleaning method. The flushing time is 10-60S, and the time is adjusted according to the amount of water. When the amount of water is large, it can be flushed for a short time, otherwise, it can be flushed for a long time. In the ultrasonic cleaning method, the thin film substrate is placed in a second container containing pure water, and the thin film substrate is oscillated and cleaned by setting an ultrasonic device. After the cleaning of the thin film substrate is completed, a detection device is used to detect the concentration of the oxidant contained in the liquid in the second container, and the pure water is replaced when it exceeds the preset value.
在步骤3中，可通过烘干法或热风吹干法干燥薄膜基板。优选采用热风吹干法，可提高薄膜基板的干燥效率，同时避免薄膜基板上产生水纹。In step 3, the thin film substrate may be dried by a drying method or a hot air drying method. The hot air drying method is preferably used, which can improve the drying efficiency of the film substrate and avoid water marks on the film substrate at the same time.
在步骤4中，可通过喷涂法或者辊涂法或者浸泡法在薄膜基板表面添加氯化镉水溶液。氯化镉水溶液中，氯化镉的质量浓度为13％～20％，以15％～18％为佳。喷涂法即通过喷头等装置将氯化镉水溶液喷涂于薄膜基板的表面；辊涂法即将粘附有氯化镉水溶液的涂辊沿着薄膜基板滚压，以将氯化镉水溶液覆盖于薄膜基板的表面；浸泡法即将薄膜基板置入盛放有氯化镉水溶液的第三容器，然后将薄膜基板提出液面。In step 4, the cadmium chloride aqueous solution may be added to the surface of the thin film substrate by spraying method, roller coating method or soaking method. In the cadmium chloride aqueous solution, the mass concentration of cadmium chloride is 13% to 20%, preferably 15% to 18%. The spraying method is to spray the cadmium chloride aqueous solution on the surface of the film substrate through the nozzle and other devices; the roller coating method is to roll the coating roller with the cadmium chloride aqueous solution along the film substrate to cover the cadmium chloride aqueous solution on the film substrate. The immersion method is to put the film substrate into a third container containing an aqueous solution of cadmium chloride, and then lift the film substrate out of the liquid surface.
上述实施例只是本发明的优选方案，本发明还可有其他实施方案。本领域的技术人员在不违背本发明精神的前提下还可作出等同变形或替换，这些等同的变型或替换均包含在本申请权利要求所设定的范围内。The above embodiments are only preferred solutions of the present invention, and the present invention may also have other embodiments. Those skilled in the art can also make equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope set by the claims of the present application.
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Application publication date: 20190726 |