WO2020006795A1 - 利用臭氧实现碱性体系对硅片刻蚀抛光的方法及设备 - Google Patents

利用臭氧实现碱性体系对硅片刻蚀抛光的方法及设备 Download PDF

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WO2020006795A1
WO2020006795A1 PCT/CN2018/097574 CN2018097574W WO2020006795A1 WO 2020006795 A1 WO2020006795 A1 WO 2020006795A1 CN 2018097574 W CN2018097574 W CN 2018097574W WO 2020006795 A1 WO2020006795 A1 WO 2020006795A1
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silicon wafer
tank
ozone
water
polishing
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PCT/CN2018/097574
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English (en)
French (fr)
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左国军
任金枝
李雄朋
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常州捷佳创精密机械有限公司
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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
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02013—Grinding, lapping
    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02019—Chemical etching
    • 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
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H01L21/67086—Apparatus for fluid treatment for etching for wet etching with the semiconductor substrates being dipped in baths or vessels
    • 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 present invention relates to the technical field of photovoltaic cells, and in particular, to a method and equipment for etching and polishing silicon wafers by using an alkaline system to realize an alkaline system.
  • the production process of conventional solar cells generally includes: texturing, diffusion, etching to remove PSG, coating, screen printing and sintering, test and sorting, etc .; some high-efficiency cells also include INK, laser etching, annealing, and atomic layer deposition. Alumina plating, PECVD, laser drilling, etc. are involved in high-efficiency battery steps.
  • the existing etching PSG removal process usually uses a mixed solution of HNO3 and HF to etch the lower surface and edges of the diffused silicon wafer to remove the N-type silicon at the edges, so that the upper and lower surfaces of the silicon wafer are insulated from each other.
  • To remove PSG is to use HF to remove the phosphosilicate glass on the surface of the silicon wafer to avoid the recombination of electrons in the emission region, which will reduce the lifetime of the minority carrier and reduce the efficiency of the battery.
  • the environmental protection problem is serious.
  • the acid etching chemical consumes a large amount, and the production cost is high.
  • the existing equipment often uses belts or rollers to convey silicon wafers for etching, and defects such as black spots, belt marks, roller marks, or dirty films are easy to appear on silicon wafers.
  • the defect rate of PERC batteries is very high, and such equipment is no longer suitable. Application on the market.
  • the present invention proposes a method and equipment for etching and polishing silicon wafers using an alkaline system using ozone.
  • the method uses ozone to clean silicon wafers, which can thoroughly clean the surface of the silicon wafers.
  • the lower surface of the silicon wafer is etched and polished by the lye and tank equipment, which is safe and environmentally friendly, low in cost, and good in quality.
  • the technical solution adopted by the present invention is to design a method for etching and polishing silicon wafers by using an alkaline system to realize the alkaline system.
  • the upper surface of the silicon wafer is covered with a PSG layer, and the PSG layer has been removed from the lower surface and side edges of the silicon wafer, including:
  • Step 1 The silicon wafer is placed in a first ozone cleaning tank, and the silicon wafer is immersed in a mixed solution containing ozone in the first ozone cleaning tank for cleaning;
  • Step 2 Put the silicon wafer in the first water tank, and soak the silicon wafer in the deionized water in the first water tank to clean;
  • Step 3 Put the silicon wafer into the etching polishing bath, soak the silicon wafer in the alkaline solution in the etching polishing bath, and perform etching polishing on the lower surface and side edges of the silicon wafer;
  • Step 4 Put the silicon wafer into the cleaning tank group for cleaning
  • Step 5 Put the silicon wafer into the pickling tank, and soak the silicon wafer in the acid solution in the pickling tank for pickling;
  • Step 6 Wash the silicon wafer in a water washing tank
  • Step 7. Put the silicon wafer in the drying tank group to dry.
  • the cleaning tank group in step 4 includes a second water tank, a second ozone cleaning tank and a third water tank arranged in this order.
  • Step 4 includes: step 4.1, cleaning the silicon wafer in the second water tank; step 4.2, cleaning the silicon wafer in the second ozone cleaning tank; step 4.3, cleaning the silicon wafer in the third water tank.
  • a mixed solution of HCl, ozone and deionized water is used in the first ozone cleaning tank in step 1.
  • concentration of HCl is 0.01% -0.3%
  • concentration of ozone is 10-50PPM
  • reaction temperature is 20 ° C to 40 ° C
  • reaction time is More than 30 seconds.
  • step 4 a mixed solution of HCl, HF, ozone and deionized water is used in the second ozone cleaning tank.
  • concentration of HCl is 0.01% -0.3%
  • concentration of HF is 0% -20%
  • concentration of ozone is 10-80PPM.
  • the temperature is 20 ° C to 40 ° C, and the reaction time is greater than 60 seconds.
  • KOH solution and polishing additive or NaOH solution and polishing additive are used for etching the lye in the polishing bath.
  • concentration of KOH or NaOH is 0.5% -10%
  • temperature of the lye is 60 °C -80 °C
  • reaction time is 60 seconds. -240 seconds.
  • the drying tank group in step 7 includes a slow lifting trough and a drying trough arranged in sequence;
  • Step 7 includes: step 7.1, placing the silicon wafer in a slow-drawing trough, immersing the silicon wafer in high-purity water, and slowly pulling the silicon wafer out of the water; step 7.2, placing the silicon wafer in a drying trough for drying.
  • the temperature of the high-purity water in the slow-pulling tank is 60 ° C to 80 ° C.
  • the invention also proposes a device for etching and polishing silicon wafers using an alkaline system by using ozone.
  • the device includes a trough-type device.
  • a first ozone-cleaning tank, a first water tank, an etching-polishing tank, and cleaning are sequentially arranged in the trough-type device.
  • the silicon wafer is placed in a flower basket, and the flower basket is sequentially put into the first ozone cleaning tank to the drying tank group by a robot hand.
  • the equipment also includes: a chain device for removing the PSG layer on the lower surface and side edges of the silicon wafer.
  • the chain device is sequentially arranged with a spray water tank, a front pickling tank, a flush water tank, a front drying tank, and a shower.
  • a spray device is arranged above the water receiving tank, and a flush device is arranged above the flushing water tank.
  • the silicon wafer is horizontally transmitted by several rollers and then passes through the spray water tank to the front drying tank.
  • the liquid level in the front pickling tank is higher than the roller.
  • the lowest point of the roller is lower than the highest point of the wheel.
  • the device also includes a transfer device that connects the chain device and the trough device, and the transfer device transfers the silicon wafer from the unloading position of the chain device to the feeding position of the trough device.
  • the present invention has the following advantages:
  • the present invention uses a mixed solution containing ozone to clean the silicon wafer.
  • Ozone has stronger oxidizing power and can thoroughly clean the surface of the silicon wafer.
  • the invention adopts alkaline solution to etch and polish the silicon wafer, realize zero emission of nitrogen, safety and environmental protection, and low chemical consumption;
  • the groove-type equipment is used for etching and polishing, which effectively avoids various quality problems caused by the contact between the silicon wafer and the tooling fixture;
  • the chain device is used to remove the PSG layer on the lower surface and side edges of the silicon wafer, which effectively protects the PN junction on the upper surface of the silicon wafer and improves the quality of the finished PERC battery.
  • FIG. 1 is a schematic view of a process flow of an etching polishing method in the present invention
  • FIG. 2 is a schematic top view of the etching and polishing equipment in the present invention
  • FIG. 3 is a schematic structural diagram of an etching polishing tank or an acid cleaning tank in the present invention.
  • FIG. 4 is a schematic structural diagram of a water washing tank in the present invention.
  • FIG. 5 is a schematic structural diagram of a clean wind down-pressure system and an air suction system in the present invention.
  • the invention deals with the etching and polishing of the non-diffusive surface during the manufacturing process of crystalline silicon cell wafers.
  • the upper surface of the silicon wafer is a PN junction layer and a PSG layer, and the lower surface and side edges are also There are a small amount of excess PN junction layer and PSG layer. These excess PSG layers need to be completely removed before etching and polishing, and the upper PSG layer needs to be retained.
  • the removal method can use a chain device to remove the PSG layer.
  • the method provided by the present invention includes:
  • Step 1 Put the silicon wafer into the first ozone cleaning tank, soak the silicon wafer in the ozone-containing mixed solution in the first ozone cleaning tank to clean it, remove the pollutants on the surface of the silicon wafer, and form a layer on the surface of the silicon wafer. An oxide layer, through which the PSG layer on the upper surface of the silicon wafer is protected,
  • a mixed solution of HCl, ozone and deionized water is used in the first ozone cleaning tank.
  • the concentration of HCl is 0.01% -0.3%, and the concentration of ozone is 10-50 PPM.
  • the mixed solution is prepared by dissolving HCl and ozone in deionized water. A lower concentration will not have the effect of cleaning surface contaminants.
  • the reaction temperature is 20 ° C to 40 ° C, and the reaction time is longer than 30 seconds. If the reaction time is too long, the alkaline solution will damage the PSG layer on the upper surface of the silicon wafer, resulting in subsequent etching. The upper surface is also polished during the polishing process, resulting in a poor appearance of the silicon wafer. Similarly, if the concentration is too high and the temperature is too high, the PSG layer on the upper surface of the silicon wafer will be damaged, and the protection effect will not be achieved, resulting in a poor appearance of the silicon wafer.
  • Step 2 The silicon wafer is placed in the first water tank, and the silicon wafer is immersed in the high-purity deionized water in the first water tank and washed to remove alkali residues on the surface of the silicon wafer.
  • the reaction temperature is normal temperature.
  • Step 3 Put the silicon wafer into the etching polishing bath, soak the silicon wafer in the alkali solution in the etching polishing bath, and etch the lower surface and side edges of the silicon wafer to insulate the upper and lower surfaces of the silicon wafer and polish the lower surface.
  • a mixed solution of a KOH solution and a polishing additive or use a mixed solution of a NaOH solution and a polishing additive.
  • the concentration of KOH or NaOH is 0.5% to 10%
  • the volume of KOH or NaOH is 5 to 20 liters
  • the volume of polishing additives is 1 to 5 liters
  • the total volume of the etching polishing tank is 300 to 400 liters
  • the temperature of the lye It needs to be within 60 °C ⁇ 80 °C, the temperature is too low to achieve the polishing effect, and the temperature is too high, the reaction will be very violent, resulting in uneven local etching and polishing on the lower surface, and the upper surface effect will be destroyed.
  • the reaction time should be within 60 seconds to 240 seconds. If the reaction time is too long, the upper surface effect will be destroyed, and if the reaction time is too short, the polishing effect will not be achieved.
  • Step 4 The silicon wafer is cleaned in a cleaning tank group to remove contaminants on the surface of the silicon wafer.
  • the cleaning tank group includes a second ozone cleaning tank, and the silicon wafer is put into a mixed solution containing ozone in the second ozone cleaning tank for cleaning.
  • step 4 includes: step 4.1, washing the silicon wafer in a second water tank to remove chemical residue on the surface of the silicon wafer, and the reaction temperature is from room temperature to high temperature; step 4.2, placing the silicon wafer Wash in the second ozone cleaning tank to remove silicon wafer surface additives, pollutants, metal particles, etc.
  • a mixed solution of HCl, HF, ozone and deionized water is used in the second ozone cleaning tank, and the concentration of HCl is 0.01% -0.3% HF concentration is 0% -20%, ozone concentration is 10-80PPM, HCl, HF and ozone are dissolved in deionized water to make a mixed solution, the reaction temperature is 20 ° C to 40 ° C, the reaction time is greater than 60 seconds, the time is too long The short cleaning effect is not good, and the ozone concentration is too low to achieve the cleaning effect.
  • Step 4.3 Put the silicon wafer in the third water tank to clean it to remove the residual ozone solution on the surface of the silicon wafer.
  • the reaction temperature is from normal temperature to 50 ° C and the reaction time is 60. Seconds to 180 seconds.
  • Step 5 Mechanically lift the silicon wafer flower basket into the pickling tank, and soak the silicon wafer in the acid solution in the pickling tank to pickle and remove the PSG layer on the upper surface of the silicon wafer.
  • the acid solution in the pickling tank uses a mixed solution of HF and HCl.
  • the concentration of HF is 1% -5%
  • the concentration of HCl is 0% -10%
  • the temperature of the acid solution is normal temperature
  • the reaction time can be 60 seconds to 180 seconds.
  • Step 6 The silicon wafer flower basket is mechanically lifted and put into a water washing tank.
  • the silicon wafer is immersed in the water of the water washing tank and washed to remove acid residue on the surface of the silicon wafer.
  • the reaction temperature is normal temperature to 50 ° C, and the reaction time can be 60 seconds to 180 seconds.
  • Step 7 The silicon wafer flower basket is mechanically lifted and put into a drying tank group for drying.
  • the drying tank group includes a slow-lifting tank and a drying tank arranged in order.
  • Step 7 includes: Step 7.1: Put the silicon wafer into the slow-drawing trough, soak the silicon wafer in high-purity water, and slowly pull the silicon wafer out of the water, so that the water is separated from the surface of the silicon wafer and the flower basket as much as possible, which can shorten the drying process.
  • this step is to pretreat the silicon wafer and silicon wafer flower basket before drying.
  • the temperature of the high-purity water needs to be within the range of room temperature to 70 ° C, and the dehydration effect is good. drying.
  • the present invention uses an alkaline solution to polish and etch a silicon wafer.
  • the effect is better than acid polishing.
  • Alkaline polishing etch can flatten the suede tower tip on the back of the battery chip, the back is flat, the passivation effect is good, and the back reflectivity is high.
  • the back-field contact has improved significantly, and the cell efficiency has improved to some extent.
  • the invention also proposes a device for etching and polishing silicon wafers using an alkaline system using ozone.
  • the device for etching and polishing silicon wafers using an alkaline system using ozone is called a total device.
  • the total equipment includes a trough equipment 3, and steps 1 to 7 in the above method are implemented by the trough equipment.
  • a first ozone cleaning tank, a first water tank, an etching polishing tank, a cleaning tank group, a pickling tank, a water cleaning tank and a drying tank group are arranged in order in the tank equipment 3, and the cleaning tank group includes a second water tank.
  • the second ozone cleaning tank and the third water tank, and the drying tank group include a slow lifting tank and a drying tank.
  • the silicon wafer 4 is placed in the flower basket 5, and the flower basket 5 is sequentially put into the first ozone cleaning tank to the drying tank by a robot hand.
  • the first water tank, the second water tank and the third water tank are provided with a bubble function and an overflow function.
  • the bubbling control mode can be set to have basket bubbling or no basket bubbling. Basket bubbling refers to bubbling only when there is a flower basket in the water tank, and no bubbling without a flower basket. Bubbling when in a flower basket. Do not bubbling when there is a flower basket. Bubbling is achieved by the bubbling tube passing into the water tank.
  • the side wall of the water tank is provided with a water overflow port. As the reaction proceeds, new deionized water needs to be added to the water tank. When the deionized water in the water tank exceeds the water overflow port, the excess deionized water will pass through. The water overflow port overflows to realize the renewal of the deionized water and keep the deionized water clean.
  • the etching polishing tank has a bubbling function, an overflow function, and a circulation function.
  • the bubbling function is consistent with the bubbling function of the above water tank.
  • the bubbling tube 9 is passed into the water tank. Bubble tube.
  • the etching and polishing tank includes: a main tank 6, a sub tank 7 surrounding the main tank 6, a circulation pump 8 for pumping liquid in the sub tank 7 to the main tank 6, and a working interface of the circulation pump 8 is connected to the pipeline
  • the main tank 6 and the auxiliary tank 7, the side wall of the main tank 6 is provided with a chemical liquid overflow port, and the auxiliary tank 7 is used to receive the alkaline liquid overflowing from the chemical liquid overflow port.
  • the circulation pump 8 pumps liquid from the auxiliary tank 7 into the main tank 6, and the main tank 6 is also provided with a flow equalizing plate 10,
  • the current equalizing plate 10 divides the main tank 6 into an upper cavity and a lower cavity.
  • the circulation pump 8 draws the alkali liquid from the auxiliary groove 7 into the lower cavity.
  • the liquid flows through the current equalizing plate to the upper cavity to achieve a uniform alkaline solution. effect.
  • the pickling tank also has a bubbling function, an overflow function, and a circulation function, and its structure is consistent with the etching polishing tank.
  • the first ozone cleaning tank, the first water tank, the second water tank, the third water tank, the etching polishing tank, the second ozone cleaning tank and the slow lifting tank all have heating devices, and the liquid in the tank is heated by the heating devices.
  • the washing tank is an underwater submersible tank.
  • a horizontal transfer mechanism 11 is provided in the washing tank.
  • a partition plate 12 is provided above the washing tank. The lower portion of the partition plate 12 is located in the middle of the washing tank and extends below the liquid level. It holds silicon wafers.
  • the flower basket 4 is placed on the horizontal transfer mechanism 11, and the flower basket 5 is transferred from one side of the partition plate 12 to the other side in water. The structure is described in detail in Patent No. 200820094928.0, and will not be repeated here.
  • Both the slow lifting trough and the drying trough are designed with a clean wind down-pressing system.
  • the clean wind down-pressing system specifically refers to setting an air inlet chamber 14 above the tank 13 and a floating fan in the air inlet chamber 14. The fan sucks the air in the environment into the air cavity 14, and the air outlet of the air inlet cavity 14 is set downward.
  • the air inlet cavity 14 is provided with a uniform flow plate and a filter. After the air passes through the uniform flow plate, it passes through the filter and exits. The air outlet spouted.
  • An air suction system is arranged around the slow lifting groove and the drying groove.
  • the air suction system specifically arranges a circle of pipes 15 around the groove body 13, and a certain number of small holes are designed in the pipes. 15 is connected to the exhaust duct 16, and an exhaust device is arranged in the exhaust duct 16.
  • the combination of the down-pressure air system and the air suction system can form a wind curtain, which completely isolates the inside and outside of the tank 13 to prevent unclean air from entering the tank 13 and improve the quality of the silicon wafer.
  • the total equipment also includes: a chain-type equipment 1.
  • the pre-processing of the silicon wafer 4 in the above method is processed by a chain-type equipment.
  • the chain-type equipment 1 is used to remove the PSG layer on the lower surface and side edges of the silicon wafer 4.
  • the spraying water tank, the front pickling tank, the flushing water tank, and the front drying tank are arranged in order in the chain device 1.
  • the spraying water tank is provided with a spray device above the flushing water tank and the flushing water tank is provided with
  • the silicon wafer 4 is horizontally transferred by several rollers and sequentially passes through the spray water tank to the front drying tank.
  • Use a spray device to uniformly spray out ion water to cover the upper surface of the silicon wafer 4, that is, the diffusion surface of the base silicon wafer.
  • the water film can be evenly spread on the upper surface of the silicon wafer 4, and the amount of water is about 5mg-8mg.
  • the HF solution in the front pickling tank is used to remove the PSG layer on the lower surface and side edges of the silicon wafer 4, the mass fraction of HF is about 2% -8%, and the reaction temperature is room temperature; After the upper surface of the silicon wafer 4 is rinsed, the silicon wafer is dried.
  • the liquid level in the front pickling tank is higher than the lowest point of the roller and lower than the highest point of the roller, preferably the liquid level is at a height of 1/3 to 2/3 above the axis of the roller, that is, below the base silicon wafer.
  • the surface can directly contact the drive shaft roller, and the roller walks with liquid. During the walking, the lower surface of the silicon wafer chemically reacts with the HF solution to achieve the removal of the PSG on the back.
  • the upper surface of the silicon wafer 4 is protected by a water film and does not react with the HF solution. Contact, no chemical reaction occurs.
  • the total equipment also includes: a transfer device 2 connecting the chain device 1 and the trough device 3, the transfer device 2 transfers the silicon wafer 4 from the unloading position of the chain device 1 to the feeding position of the trough device 3, and the transfer device 2 Structures such as conveyor belts, and robotic components such as robots can also be used.

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Abstract

本发明公开了一种利用臭氧实现碱性体系对硅片刻蚀抛光的方法及设备，该方法包括：步骤1、使用臭氧溶液对硅片进行表面处理；2、使用去离子水对硅片进行清洗；3、使用碱液对硅片的下表面及侧面边缘进行刻蚀抛光；4、清洗硅片去除表面污染物；5、使用酸液对硅片进行酸洗；6、清洗硅片去除残留药液；7、烘干硅片。该设备包括槽式设备、链式设备和搬送设备。本发明利用臭氧实现碱性体系对硅片的刻蚀抛光，安全环保、成本低且品质好。

Description

利用臭氧实现碱性体系对硅片刻蚀抛光的方法及设备 技术领域
本发明涉及光伏电池技术领域，尤其涉及一种利用臭氧实现碱性体系对硅片刻蚀抛光的方法及设备。
背景技术
常规太阳能电池的生产流程一般包括：制绒、扩散、刻蚀去PSG、镀膜、丝网印刷及烧结、测试分选等工序；部分高效电池还增加了INK、激光刻蚀、退火、原子层沉积背面镀氧化铝薄膜、PECVD、激光开孔等涉及到高效电池的步骤。
现有的刻蚀去PSG工艺通常是利用HNO3和HF的混合溶液对扩散后硅片下表面和边缘进行腐蚀，去除边缘的N型硅，使得硅片的上下表面相互绝缘。去PSG是利用HF去除硅片表面的磷硅玻璃，避免发射区电子的复合，导致少子寿命的降低，进而降低电池片效率，但这种酸刻蚀方法产生的废液、废气不能直接排放，环保问题严重，另外酸刻蚀的化学品耗量大，生产成本高。
另外，现有设备多采用皮带或滚轮传送硅片进行刻蚀，硅片上容易出现黑斑、皮带印、滚轮印或脏片等缺陷，PERC电池的不良率非常高，这种设备已不适合应用在市场上。
发明内容
为了解决现有技术中存在的上述缺陷，本发明提出一种利用臭氧实现碱性体系对硅片刻蚀抛光的方法及设备，该方法使用臭氧对硅片进行清洗，能够彻底清洁硅片表面，再通过碱液及槽式设备对硅片进行下表面刻蚀抛光处理，安 全环保、成本低且成品质量好。
本发明采用的技术方案是，设计一种利用臭氧实现碱性体系对硅片刻蚀抛光的方法，硅片的上表面覆盖有PSG层，硅片的下表面及侧面边缘已去除PSG层，包括：
步骤1、将硅片放入第一臭氧清洗槽，硅片浸泡在第一臭氧清洗槽内含有臭氧的混合溶液中清洗；
步骤2、将硅片放入第一水槽，硅片浸泡在第一水槽内的去离子水中清洗；
步骤3、将硅片放入刻蚀抛光槽，硅片浸泡在刻蚀抛光槽内的碱液中，对硅片下表面及侧面边缘进行刻蚀抛光；
步骤4、将硅片放入清洗槽组中清洗；
步骤5、将硅片放入酸洗槽，硅片浸泡在酸洗槽内的酸液中酸洗；
步骤6、将硅片放入水洗槽中清洗；
步骤7、将硅片放入烘干槽组中干燥。
优选的，步骤4中清洗槽组包括依次排列的第二水槽、第二臭氧清洗槽和第三水槽。步骤4包括：步骤4.1、将硅片放入第二水槽中清洗；步骤4.2、将硅片放入第二臭氧清洗槽清洗；步骤4.3、将硅片放入第三水槽中清洗。
其中，步骤1中第一臭氧清洗槽内使用HCl、臭氧和去离子水的混合溶液，HCl浓度为0.01％-0.3％，臭氧的浓度为10-50PPM，反应温度20℃到40℃，反应时间大于30秒。
步骤4中第二臭氧清洗槽内使用HCl、HF、臭氧和去离子水的混合溶液，HCl浓度为0.01％-0.3％，HF浓度为0％-20％，臭氧的浓度为10-80PPM，反应温度20℃到40℃，反应时间大于60秒。
刻蚀抛光槽内的碱液使用KOH溶液和抛光添加剂、或使用NaOH溶液和 抛光添加剂，KOH或NaOH浓度为0.5％-10％，碱液的温度为60℃-80℃，反应时间为60秒-240秒。
优选的，步骤7中烘干槽组包括依次排列的慢提拉槽和烘干槽；
步骤7包括：步骤7.1、将硅片放入慢提拉槽，硅片浸泡在高纯水中，慢慢提拉硅片出水；步骤7.2、将硅片放入烘干槽中烘干。
慢提拉槽内的高纯水温度为60℃～80℃。
本发明还提出了一种利用臭氧实现碱性体系对硅片刻蚀抛光的设备，包括：槽式设备，槽式设备内依次排列有第一臭氧清洗槽、第一水槽、刻蚀抛光槽、清洗槽组、酸洗槽、水洗槽及烘干槽组，硅片放置在花篮内，通过机械手将花篮依次放入第一臭氧清洗槽至烘干槽组中。
该设备还包括：用于去除硅片下表面及侧面边缘PSG层的链式设备，链式设备内依次排列有喷淋接水槽、前酸洗槽、冲洗接水槽、前烘干槽，喷淋接水槽的上方设有喷淋装置，冲洗接水槽的上方设有冲洗装置，硅片由若干个滚轮水平传递依次经过喷淋水槽至前烘干槽，前酸洗槽内的液位高于滚轮的最低点、低于滚轮的最高点。
该设备还包括：连接链式设备和槽式设备的搬送设备，搬送设备将硅片从链式设备的下料位置搬送至槽式设备的上料位置。
与现有技术相比，本发明具有以下优点：
1、本发明采用含有臭氧的混合溶液对硅片进行清洗，臭氧具有更强的氧化性，能够彻底清洁硅片表面；
2、本发明采用碱液对硅片进行刻蚀抛光，实现氮的零排放，安全环保且化学品耗量低；
3、采用槽式设备实现刻蚀抛光，刻蚀过程中有效避免了硅片与工装夹具接 触而带来的各种品质问题；
4、采用链式设备去除硅片下表面及侧面边缘的PSG层，有效保护硅片上表面的PN结，提高PERC电池成品质量。
附图说明
下面结合优选实施例和附图对本发明进行详细说明，其中：
图1是本发明中刻蚀抛光方法的工艺流程示意图；
图2是本发明中刻蚀抛光设备的俯视示意图；
图3是本发明中刻蚀抛光槽或酸洗槽的结构示意图；
图4是本发明中水洗槽的结构示意图；
图5是本发明中洁净风下压系统和吸风系统的结构示意图。
具体实施方式
本发明处理的是晶硅电池片生产制造过程中非扩散面的刻蚀抛光，晶硅硅片在扩散工序完成之后，硅片的上表面为PN结层及PSG层，下表面以及侧面边缘也存在少量多余的PN结层及PSG层，这些多余的PSG层在做刻蚀抛光前需要完全去除，而上表面的PSG层需要保留，去除的方法可以使用链式设备去除PSG层。
如图1所示，本发明提出的方法包括：
步骤1、将硅片放入到第一臭氧清洗槽，硅片浸泡在第一臭氧清洗槽内内含有臭氧的混合溶液中清洗，去除硅片表面的污染物，并在硅片表面形成一层氧化层，通过该氧化层保护硅片上表面的PSG层，
第一臭氧清洗槽内使用HCl、臭氧和去离子水的混合溶液，HCl浓度为 0.01％-0.3％，臭氧的浓度为10-50PPM，将HCl和臭氧溶入去离子水中制成混合溶液，如果浓度偏低会起不到清洗表面污染物的效果，反应温度20℃到40℃，反应时间大于30秒，反应时间过久会使碱液破坏硅片上表面的PSG层，导致后续的刻蚀抛光工艺中上表面也会被抛光，造成硅片外观不良。同样的，如果浓度过高、温度过高均会破坏硅片上表面的PSG层，起不到保护的效果，造成硅片外观不良。
步骤2、将硅片放入第一水槽，硅片浸泡在第一水槽内的高纯度去离子水中清洗，去除硅片表面的碱液残留，反应温度为常温。
步骤3、将硅片放入刻蚀抛光槽，硅片浸泡在刻蚀抛光槽内的碱液中，对硅片下表面及侧面边缘进行刻蚀，使得硅片上下表面绝缘以及下表面抛光，碱液使用KOH溶液和抛光添加剂的混合溶液，或使用NaOH溶液和抛光添加剂的混合溶液。
KOH或NaOH浓度为0.5％～10％，KOH或NaOH体积为5升～20升，抛光添加剂体积为1升～5升，刻蚀抛光槽的总体积为300升～400升，碱液的温度需在60℃～80℃内，温度太低达不到抛光的效果，温度太高反应就会非常剧烈，导致下表面刻蚀抛光的局部不均匀，同时会破坏上表面效果。反应时间需在60秒～240秒内，反应时间太长也会破坏上表面效果，反应时间太短也会达不到抛光的效果。
步骤4、将硅片放入清洗槽组中清洗，去除硅片表面的污染物。清洗槽组包含第二臭氧清洗槽，硅片放入第二臭氧清洗槽内含有臭氧的混合溶液中清洗。
在一较优实施例中，步骤4包括：步骤4.1、将硅片放入第二水槽中清洗，去除硅片表面的药液残留，反应温度室温到高温都可行；步骤4.2、将硅片放入第二臭氧清洗槽清洗，以去除硅片表面添加剂，污染物，金属颗粒等，第二臭 氧清洗槽内使用HCl、HF、臭氧和去离子水的混合溶液，HCl浓度为0.01％-0.3％，HF浓度为0％-20％，臭氧的浓度为10-80PPM，将HCl、HF和臭氧溶入去离子水中制成混合溶液，反应温度20℃到40℃，反应时间大于60秒，时间太短清洗效果不佳，臭氧浓度偏低起不到清洗效果；步骤4.3、将硅片放入第三水槽中清洗，去除硅片表面的臭氧混合溶液残留，反应温度常温到50℃，反应时间60秒到180秒。
步骤5、机械手提起硅片花篮放入酸洗槽，硅片浸泡在酸洗槽内的酸液中酸洗，去除硅片上表面的PSG层。酸洗槽内的酸液使用HF和HCl的混合溶液，HF浓度为1％-5％，HCl浓度为0％-10％，酸液的温度为常温，反应时间可为60秒～180秒。
步骤6、机械手提起硅片花篮放入水洗槽，硅片浸泡在水洗槽的水中清洗，去除硅片表面的酸液残留，反应温度常温到50℃，反应时间可为60秒到180秒。
步骤7、机械手提起硅片花篮放入烘干槽组干燥。
较优的，烘干槽组包括依次排列的慢提拉槽和烘干槽。步骤7包括：步骤7.1、将硅片放入慢提拉槽，硅片浸泡在高纯水中，慢慢提拉硅片出水，使得水尽可能的脱离硅片表面及花篮，能够起到缩短烘干时间的目的，该步是在烘干前对硅片及硅片花篮做预处理用，高纯水的温度需要在室温～70℃内，脱水效果好；步骤7.2、将硅片放入烘干槽中烘干。
本发明采用碱液对硅片进行抛光刻蚀，其效果比酸抛好，碱抛光刻蚀能把电池片背面绒面塔尖削平，背面比较平坦，钝化效果较好，背反射率高，背场接触改善明显，电池片效率有一定的提升。
本发明还提出了一种利用臭氧实现碱性体系对硅片刻蚀抛光的设备，为便于描述且避免混淆，将该利用臭氧实现碱性体系对硅片刻蚀抛光的设备称为总 设备。总设备包括：槽式设备3，上述方法中的步骤1至步骤7通过槽式设备实现。
具体来说，槽式设备3内依次排列有第一臭氧清洗槽、第一水槽、刻蚀抛光槽、清洗槽组、酸洗槽、水洗槽及烘干槽组，清洗槽组包括第二水槽、第二臭氧清洗槽、第三水槽，烘干槽组包括慢提拉槽和烘干槽。硅片4放置在花篮5内，通过机械手将花篮5依次放入第一臭氧清洗槽至烘干槽中。
第一水槽、第二水槽和第三水槽均设有鼓泡功能和溢流功能。其中鼓泡的控制方式可设置为有篮鼓泡或者无篮鼓泡，有篮鼓泡是指水槽内有花篮的时候才鼓泡、没有花篮不鼓泡，无篮鼓泡是指水槽内没有花篮时鼓泡，有花篮时不要鼓泡，鼓泡是由鼓泡管通入水槽中实现。水槽的侧壁上设有水溢流口，随着反应的进行，需要补充新的去离子水进入到水槽中，当水槽的去离子水超过水溢流口时，多余的去离子水会通过水溢流口溢流掉，以此来实现去离子水的更新，保持去离子水的洁净。
刻蚀抛光槽设有鼓泡功能、溢流功能和循环功能，其鼓泡功能与上述水槽的鼓泡功能一致，鼓泡管9通入水槽中实现，水槽内设有外接鼓泡器的鼓泡管。刻蚀抛光槽包括：主槽6、围设于主槽6外侧的副槽7、将副槽7内液体抽至主槽6内的循环泵8，循环泵8的工作接口通过管路连接到主槽6和副槽7，主槽6的侧壁设有药液溢流口，副槽7用于承接从药液溢流口溢出的碱液，当主槽6的碱液超过药液溢流口时，多余的碱液会通过药液溢流口流到副槽7中，循环泵8从副槽7抽液打入到主槽6，主槽6中还设有均流板10，通过均流板10将主槽6分为上腔和下腔，循环泵8将副槽7中的碱液抽到下腔中，液体经过均流板流至上腔，以此来达到均匀碱液的作用。
酸洗槽也设有鼓泡功能、溢流功能和循环功能，其结构与刻蚀抛光槽一致。
第一臭氧清洗槽、第一水槽、第二水槽、第三水槽、刻蚀抛光槽、第二臭氧清洗槽和慢提拉槽均带有加热器件，通过加热器件对槽中液体进行加热。
水洗槽为水下潜送槽，水洗槽内设有水平传送机构11，水洗槽的上方设有隔板12，隔板12下部位于水洗槽的中间位置并延伸至液面以下，承装硅片4的花篮放置在该水平传送机构11上，从水中将花篮5由隔板12的一侧传送至另一侧，其结构在专利号200820094928.0中有详细介绍，在此不做赘述。
慢提拉槽和烘干槽均设计有洁净风下压系统，洁净风下压系统具体是指在槽体13上方设置进风腔14，进风腔14内设有幽浮扇，通过幽浮扇将环境中的空气吸入进风腔14中，进风腔14的出风口向下设置，进风腔14内设有匀流板和过滤器，空气经过匀流板后再经过过滤器从出风口喷出。
慢提拉槽和烘干槽的周围均排布了一圈吸风系统，吸风系统具体是在槽体13周围排布了一圈管道15，管道15上设计了一定数量的小孔，管道15与排风管道16相连接，排风管道16内设有抽风器件。下压风系统与吸风系统组合起来可形成一道风帘，此风帘将槽体13内外完全隔离，防止非洁净的风进入到槽体13内，提高硅片品质。
总设备还包括：链式设备1，上述方法中硅片4的前期处理通过链式设备处理，链式设备1用于去除硅片4下表面及侧面边缘PSG层。
具体来说，链式设备1内依次排列有喷淋接水槽、前酸洗槽、冲洗接水槽、前烘干槽，喷淋接水槽的上方设有喷淋装置，冲洗接水槽的上方设有冲洗装置，硅片4由若干个滚轮水平传递依次经过喷淋水槽至前烘干槽。利用喷淋装置均匀的喷淋出去离子水覆盖在硅片4的上表面，即基底硅片的扩散面，其中水膜能够均匀的平铺在硅片4的上表面，水量约为5mg-8mg；然后，利用前酸洗槽内的HF溶液去除硅片4的下表面及侧面边缘的PSG层，HF的质量分数大约在 2％-8％，反应温度为室温；然后，利用去离子水进行冲洗硅片4的上表面后，对硅片烘干处理。前酸洗槽内的液位高于滚轮的最低点、低于滚轮的最高点，优选是液位高度在滚轮轴心位置上方的1/3～2/3高度处，即基底硅片的下表面能够直接接触传动轴滚轮，由滚轮带液行走，行走过程中硅片的下表面与HF溶液发生化学反应，实现去除背面PSG的作用，硅片4的上表面由水膜保护不与HF溶液接触，不发生化学反应。
总设备还包括：连接链式设备1和槽式设备3的搬送设备2，搬送设备2将硅片4从链式设备1的下料位置搬送至槽式设备3的上料位置，搬送设备2采用传送带等结构，也可以采用机械手等自动化部件。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种利用臭氧实现碱性体系对硅片刻蚀抛光的方法，所述硅片的上表面覆盖有PSG层，所述硅片的下表面及侧面边缘已去除PSG层，其特征在于包括：
    步骤1、将硅片放入第一臭氧清洗槽，硅片浸泡在第一臭氧清洗槽内含有臭氧的混合溶液中清洗；
    步骤2、将硅片放入第一水槽，硅片浸泡在第一水槽内的去离子水中清洗；
    步骤3、将硅片放入刻蚀抛光槽，硅片浸泡在刻蚀抛光槽内的碱液中，对硅片下表面及侧面边缘进行刻蚀抛光；
    步骤4、将硅片放入清洗槽组中清洗；
    步骤5、将硅片放入酸洗槽，硅片浸泡在酸洗槽内的酸液中酸洗；
    步骤6、将硅片放入水洗槽中清洗；
    步骤7、将硅片放入烘干槽组中干燥。
  2. 如权利要求1所述的方法，其特征在于，所述步骤4中清洗槽组包括依次排列的第二水槽、第二臭氧清洗槽和第三水槽；
    所述步骤4包括：步骤4.1、将硅片放入第二水槽中清洗；步骤4.2、将硅片放入第二臭氧清洗槽清洗；步骤4.3、将硅片放入第三水槽中清洗。
  3. 如权利要求1所述的方法，其特征在于，所述步骤1中第一臭氧清洗槽内使用HCl、臭氧和去离子水的混合溶液，HCl浓度为0.01％-0.3％，臭氧的浓度为10-50PPM，反应温度20℃到40℃，反应时间大于30秒。
  4. 如权利要求2所述的方法，其特征在于，所述步骤4中第二臭氧清洗槽内使用HCl、HF、臭氧和去离子水的混合溶液，HCl浓度为0.01％-0.3％，HF浓度为0％-20％，臭氧的浓度为10-80PPM，反应温度20℃到40℃，反应时间大于60秒。
  5. 如权利要求1所述的方法，其特征在于，所述刻蚀抛光槽内的碱液内使用KOH溶液和抛光添加剂、或使用NaOH溶液和抛光添加剂，KOH或NaOH浓度为0.5％-10％，碱液的温度为60℃-80℃，反应时间为60秒-240秒。
  6. 如权利要求1所述的方法，其特征在于，所述步骤7中烘干槽组包括依次排列的慢提拉槽和烘干槽；
    步骤7包括：步骤7.1、将硅片放入慢提拉槽，硅片浸泡在高纯水中，慢慢提拉硅片出水；步骤7.2、将硅片放入烘干槽中烘干。
  7. 如权利要求6所述的方法，其特征在于，所述慢提拉槽内的高纯水温度为常温～75℃。
  8. 一种利用臭氧实现碱性体系对硅片刻蚀抛光的设备，包括：槽式设备，其特征在于，所述槽式设备内依次排列有第一臭氧清洗槽、第一水槽、刻蚀抛光槽、清洗槽组、酸洗槽、水洗槽及烘干槽组，所述硅片放置在花篮内，通过机械手将花篮依次放入第一臭氧清洗槽至烘干槽组中。
  9. 如权利要求8所述的设备，其特征在于，还包括：用于去除硅片下表面及侧面边缘PSG层的链式设备，所述链式设备内依次排列有喷淋接水槽、前酸洗槽、冲洗接水槽、前烘干槽，所述喷淋接水槽的上方设有喷淋装置，所述冲洗接水槽的上方设有冲洗装置，所述硅片由若干个滚轮水平传递依次经过喷淋水槽至前烘干槽，所述前酸洗槽内的液位高于所述滚轮的最低点、低于所述滚轮的最高点。
  10. 如权利要求9所述的设备，其特征在于，还包括：连接链式设备和槽式设备的搬送设备，所述搬送设备将硅片从链式设备的下料位置搬送至槽式设备的上料位置。
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