CN102544208A - High-temperature dry method double-side oxidizing process for crystal silicon wafer - Google Patents
High-temperature dry method double-side oxidizing process for crystal silicon wafer Download PDFInfo
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- CN102544208A CN102544208A CN2011104462434A CN201110446243A CN102544208A CN 102544208 A CN102544208 A CN 102544208A CN 2011104462434 A CN2011104462434 A CN 2011104462434A CN 201110446243 A CN201110446243 A CN 201110446243A CN 102544208 A CN102544208 A CN 102544208A
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Abstract
The invention discloses a high-temperature dry method double-side oxidizing process for a crystal silicon wafer. The process comprises the following steps of: (1) feeding a boat: loading the crystal silicon wafer into a boat, and propelling into an oxidation furnace tube; (2) stabilizing temperature: adjusting the temperature in the oxidizing furnace tube; (3) oxidizing: injecting oxygen and nitrogen into an oxidizing furnace for oxidizing the silicon wafer; (4) stabilizing: stopping supplying oxygen to the oxidizing furnace after oxidation, and adjusting the flow of the nitrogen and the temperature in the oxidizing furnace; and (5) withdrawing the boat: withdrawing a quartz boat or a graphite boat loaded with the oxidized silicon wafer from the oxidizing furnace tube. The process is low in cost and low in process equipment requirement, and does not require to add additional equipment; and the crystal silicon wafer is arranged in the oxidizing furnace tube for growing a layer of oxidation film by oxidizing with a high-temperature dry method before a passivation film is coated to form a double-layer film with superior performance together with a silicon nitride film, and the double-layer film has superior passivation performance and anti-reflection performance.
Description
Technical field
The invention belongs to solar cell and make the field, be specifically related to the two-sided oxidation technology of a kind of crystal silicon chip high-temperature dry.
Background technology
The battery production flow process of conventional crystal silicon chip comprises following operation such as making herbs into wool-diffusion-etching-remove PSG-plated film-silk-screen etc., but in monocrystalline silicon battery production, has following problem in the prior art: (1) can't form excellent passivation effect; (2) can only the deposited monolayers silicon nitride film, can't realize excellent reflection preventing ability.
Summary of the invention
The object of the present invention is to provide the two-sided oxidation technology of a kind of crystal silicon chip high-temperature dry; This technology cost is low; Process equipment requires simple, and need not to increase additional apparatus, and it is through placing oxidation boiler tube high-temperature dry oxidation growth layer oxide film with crystal silicon chip before the plating passivating film; With the duplicature of silicon nitride film formation excellent performance, this duplicature possesses excellent passivation and reflection preventing ability.
Above-mentioned technical purpose of the present invention realizes through following technical scheme: the two-sided oxidation technology of a kind of crystal silicon chip high-temperature dry may further comprise the steps:
(1) advances boat: with advancing behind the crystalline silicon boat on chip in the oxidation furnace pipe;
(2) temperature stabilization: the temperature in the adjustment oxidation boiler tube;
(3) oxidation: injection oxygen and nitrogen carry out oxidation to silicon chip in oxidation furnace;
(4) stable: oxidation stops oxygen supply in oxidation furnace after accomplishing, and regulates the flow of nitrogen and the temperature in the oxidation furnace;
(5) move back boat: the quartz boat or the graphite boat of silicon chip withdraws from from the oxidation boiler tube after the oxidation being equipped with.
The crystal silicon chip that adopts in the step of the present invention (1) is a monocrystalline silicon piece.
Silicon chip according to the invention is earlier through diffusion and clean.
With advancing behind the crystalline silicon boat on chip in the oxidation furnace pipe, and in oxidation furnace, inject the nitrogen that is used to protect oxidation furnace in the step of the present invention (1), the flow of said nitrogen is 25000 ~ 30000cm
3/ min.
The used time is 5 ~ 10min in the oxidation furnace pipe with advancing behind the crystalline silicon boat on chip in the step of the present invention (1), and the temperature in the adjustment oxidation furnace is 700 ~ 750 ℃.
Temperature to 700 ~ 750 in the step of the present invention (2) in the adjustment oxidation boiler tube ℃ keep 10 ~ 15min, inject simultaneously to be used to protect the nitrogen of oxidation furnace, and to regulate its flow are 28000 ~ 30000 cm
3/ min.
When in oxidation furnace, injecting oxygen in the step of the present invention (3) and with nitrogen silicon chip being carried out oxidation, the flow of adjusting nitrogen and oxygen is 15000 ~ 30000 cm
3/ min regulates temperature and is 700 ~ 750 ℃ silicon chip carried out oxidation 30-60min.
Oxidation stops oxygen supply in oxidation furnace after accomplishing in the step of the present invention (4), and the flow of regulating nitrogen is 28000 ~ 30000 cm
3Temperature in/min, the oxidation furnace is 700 ~ 750 ℃ and keeps 5 ~ 10min to make the ensuing boat hot environment of moving back more stable.
Regulating the interior temperature of oxidation furnace in the step of the present invention (5) is 700 ~ 750 ℃, and nitrogen flow is 28000 ~ 30000 cm
3/ min, the quartz boat or the graphite boat of silicon chip withdraws from from the oxidation boiler tube in 5 ~ 10min after the oxidation being equipped with.
The present invention has following advantage:
(1) the present invention is directed in the manufacturing process of current crystal silicon battery, directly plating silicon nitride film of back is cleaned in the silicon chip diffusion, can't form excellent passivation effect and reflection preventing ability.Therefore; Before plated film, add thermal oxidation process one, through boiler tube high-temperature dry oxidation growth layer oxide film, said oxide-film and silicon nitride film form the duplicature system of excellent performance; This duplicature system possesses excellent inactivating performance, can promote the conversion efficiency of battery;
When (2) adopting technology of the present invention; After crystal silicon chip withdraws from from oxidation furnace; Grow fine and close at silicon chip surface; Stable oxide film carries out coating film treatment like plating individual layer or double-deck silicon nitride film to crystal silicon chip again, and the silicon nitride film that the silicon oxide film that obtains through thermal oxidation like this obtains with follow-up plated film forms the duplicature of excellent performance; The inactivating performance of this duplicature and reflection preventing ability are superior to the silicon nitride film of individual layer, and finally can promote the conversion efficiency of crystal silicon solar batteries sheet.
Description of drawings
Fig. 1 is the minority carrier life time figure that only plates the crystal silicon chip of individual layer silicon nitride film among the embodiment 1 without thermal oxidation process;
Fig. 2 is the minority carrier life time figure of the crystal silicon chip of the silica after thermal oxidation and silicon nitride duplicature among the embodiment 1;
Fig. 3 is the silicon dioxide processed among the embodiment 1 and the anti-reflective effect comparison diagram of silicon nitride duplicature and individual layer silicon nitride film; Wherein oxidation representes to have the reflectivity curve of the duplicature of silica and silicon nitride, and no-oxidation representes to have only the reflectivity curve of silicon nitride monofilm;
Fig. 4 is the crystal silicon chip of the silica after thermal oxidation and silicon nitride duplicature among the embodiment 1 and without the conversion efficiency comparison diagram of the crystal silicon chip of the silicon nitride monofilm of thermal oxidation.
Embodiment
The present invention will be described below to enumerate specific embodiment.It is pointed out that embodiment only is used for the present invention is described further, do not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
Embodiment 1
This enforcement provides the two-sided oxidation technology of monocrystalline silicon boiler tube high-temperature dry, may further comprise the steps:
(1) advances boat (Loading): will spread silicon chip after the cleaning quartz boat of packing into, and advance and expand in the oxidation boiler tube; Progradation is controlled at 5min, and temperature is set in 700 ℃, in order to protect the oxidation boiler tube and to help ensuing oxidation, needs nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 28000 cm
3/ min;
(2) temperature stabilization (Temperature stable): make the temperature complete stability to 700 ℃ in the oxidation boiler tube; The time of this process is controlled at 10 min, in order to protect the oxidation boiler tube and to help ensuing oxidation, needs nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 28000 cm
3/ min;
(3) oxidizing process (Wet oxidation growth): oxygen is fed the oxidation boiler tube carry out oxidation; Oxygen flow is controlled at 15000 cm
3/ min, temperature is set in 700 ℃, and the time of whole process is controlled at 30 min, in order to protect oxidation boiler tube and the stability and the uniformity that guarantee whole technology, needs nitrogen injection to arrive in the oxidation boiler tube, nitrogen and oxygen equivalent, flow control is at 15000cm
3/ min;
(4) stabilization process (oxidation stable) after oxidizing process is accomplished: the feasible boat hot environment of next moving back is more stable; The time of this process was controlled at 5 minutes, and temperature is set in 700 ℃, in order to protect the oxidation boiler tube, needed nitrogen injection gas in the oxidation boiler tube, and nitrogen flow is controlled at 28000 cm
3/ min;
(5) move back boat (Loading): from the oxidation boiler tube, withdraw from the quartz boat of silicon chip after the loading oxidation; The time of this process is controlled at 5min, and temperature is set in 700 ℃, in order to protect the oxidation boiler tube, needs nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 28000 cm
3/ min.
As illustrated in fig. 1 and 2; Anti-reflective effect at shortwave place silica and silicon nitride duplicature obviously is superior to the individual layer silicon nitride film, and the passivation effect that promptly has the solar cell of silica and silicon nitride duplicature is better than the passivation effect of the solar cell that the silicon nitride monofilm is only arranged.
Table 1 is through thermal oxidation with without the minority carrier life time comparison diagram of thermal oxidation
Table 2 is through thermal oxidation with without the transformation efficiency of the solar cell of thermal oxidation
| Divide into groups | Conversion efficiency |
| Without thermal oxidation | 17.95787672 |
| After the thermal oxidation | 18.05726617 |
From table 1, can find out; Increased after the thermal oxidation process, minority carrier life time is 5.134 μ s before the oxidation, and minority carrier life time is 8.171 μ s after the oxidation; Combine with follow-up plating silicon nitride film; The minority carrier life time that the individual layer silicon nitride film is only arranged is 5.58 μ s, is 21.935 μ s and the minority carrier life time of silica and silicon nitride duplicature is arranged, and minority carrier life time significantly improves; Can find out that from last table 2 and Fig. 4 through after the thermal oxidation, the transformation efficiency of solar cell is significantly improved.
Embodiment 2
Present embodiment provides the two-sided oxidation technology of monocrystalline silicon boiler tube high-temperature dry, may further comprise the steps:
(1) advances boat (Loading): will spread silicon chip after the cleaning quartz boat of packing into, and advance and expand in the oxidation boiler tube; Progradation was controlled at 10 minutes, and temperature is set in 750 degrees centigrade, in order to protect the oxidation boiler tube and to help ensuing oxidation, needed nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 30000 cc/min;
(2) temperature stabilization (Temperature stable): make the temperature complete stability to 750 degree centigrade in the oxidation boiler tube; The time of this process was controlled at 15 minutes, in order to protect the oxidation boiler tube and to help ensuing oxidation, needed nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 30000 cc/min;
(3) oxidizing process (Wet oxidation growth): oxygen is fed the oxidation boiler tube carry out oxidation; Oxygen flow is controlled at 20000 cc/min; Temperature is set in 750 degrees centigrade; The time of whole process was controlled at 60 minutes, in order to protect oxidation boiler tube and the stability and the uniformity that guarantee whole technology, needed nitrogen injection to arrive in the oxidation boiler tube; The consumption of nitrogen is less times greater than the consumption of oxygen, and flow control is in 20050 cc/min;
(4) stabilization process (oxidation stable) after oxidizing process is accomplished: the feasible boat hot environment of next moving back is more stable; The time of this process was controlled at 10 minutes, and temperature is set in 750 degrees centigrade, in order to protect the oxidation boiler tube, needed nitrogen injection gas in the oxidation boiler tube, and nitrogen flow is controlled at 30000 cc/min;
(5) move back boat (Loading): from the oxidation boiler tube, withdraw from the quartz boat of silicon chip after the loading oxidation; The time of this process was controlled at 10 minutes, and temperature is set in 750 degrees centigrade, in order to protect the oxidation boiler tube and to help ensuing oxidation, needed nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 30000 cc/min.
Embodiment 3
Present embodiment provides the two-sided oxidation technology of monocrystalline silicon boiler tube high-temperature dry, may further comprise the steps:
(1) advances boat (Loading): will spread silicon chip after the cleaning quartz boat of packing into, and advance and expand in the oxidation boiler tube; Progradation was controlled at 8 minutes, and temperature is set in 720 degrees centigrade, in order to protect the oxidation boiler tube and to help ensuing oxidation, needed nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 25000 cc/min;
(2) temperature stabilization (Temperature stable): make the temperature complete stability to 720 degree centigrade in the oxidation boiler tube; The time of this process was controlled at 12 minutes, in order to protect the oxidation boiler tube and to help ensuing oxidation, needed nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 29000 cc/min;
(3) oxidizing process (Wet oxidation growth): oxygen is fed the oxidation boiler tube carry out oxidation; Oxygen flow is controlled at 29000 cc/min; Temperature is set in 720 degrees centigrade, and the time of whole process was controlled at 45 minutes, in order to protect oxidation boiler tube and the stability and the uniformity that guarantee whole technology; Need nitrogen injection to arrive in the oxidation boiler tube; Nitrogen and oxygen equivalent, perhaps the consumption of nitrogen is less times greater than the consumption of oxygen, flow control 29000 cc/min or greater than 29000 cc/min like 30000 cc/min etc.;
(4) stabilization process (oxidation stable) after oxidizing process is accomplished: the feasible boat hot environment of next moving back is more stable; The time of this process was controlled at 8 minutes, and temperature is set in 720 degrees centigrade, in order to protect the oxidation boiler tube, needed nitrogen injection gas in the oxidation boiler tube, and nitrogen flow is controlled at 29000 cc/min;
(5) move back boat (Loading): from the oxidation boiler tube, withdraw from the quartz boat of silicon chip after the loading oxidation; The time of this process was controlled at 8 minutes, and temperature is set in 720 degrees centigrade, in order to protect the oxidation boiler tube, needed nitrogen injection to arrive in the oxidation boiler tube, and nitrogen flow is controlled at 29000 cc/min.
The present invention will be described more than to enumerate specific embodiment.It is pointed out that the foregoing description only is used for the present invention is described further, do not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
Claims (9)
1. two-sided oxidation technology of crystal silicon chip high-temperature dry is characterized in that may further comprise the steps:
(1) advances boat: with advancing behind the crystalline silicon boat on chip in the oxidation furnace pipe;
(2) temperature stabilization: the temperature in the adjustment oxidation boiler tube;
(3) oxidation: injection oxygen and nitrogen carry out oxidation to silicon chip in oxidation furnace;
(4) stable: oxidation stops oxygen supply in oxidation furnace after accomplishing, and regulates the flow of nitrogen and the temperature in the oxidation furnace;
(5) move back boat: the quartz boat or the graphite boat of silicon chip withdraws from from the oxidation boiler tube after the oxidation being equipped with.
2. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1 is characterized in that: the crystal silicon chip that adopts in the step (1) is a monocrystalline silicon piece.
3. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 2 is characterized in that: said silicon chip is earlier through diffusion and clean.
4. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1; It is characterized in that: in the step (1) with advancing behind the crystalline silicon boat on chip in the oxidation furnace pipe; And in oxidation furnace, injecting the nitrogen that is used to protect oxidation furnace, the flow of said nitrogen is 25000 ~ 30000cm
3/ min.
5. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1 is characterized in that: the used time is 5 ~ 10min in the oxidation furnace pipe with advancing behind the crystalline silicon boat on chip in the step (1), and the temperature in the adjustment oxidation furnace is 700 ~ 750 ℃.
6. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1; It is characterized in that: ℃ maintenance 10 ~ 15min of temperature to 700 ~ 750 in the step (2) in the adjustment oxidation boiler tube; Inject simultaneously and be used to protect the nitrogen of oxidation furnace, and to regulate its flow be 28000 ~ 30000 cm
3/ min.
7. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1 is characterized in that: when in oxidation furnace, injecting oxygen in the step (3) and with nitrogen silicon chip being carried out oxidation, the flow of adjusting nitrogen and oxygen is 15000 ~ 30000cm
3/ min regulates temperature and is 700 ~ 750 ℃ silicon chip carried out oxidation 30-60min.
8. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1 is characterized in that: oxidation stops oxygen supply in oxidation furnace after accomplishing in the step (4), and the flow of regulating nitrogen is 28000 ~ 30000 cm
3Temperature in/min, the oxidation furnace is 700 ~ 750 ℃ and keeps 5 ~ 10min to make the ensuing boat hot environment of moving back more stable.
9. the two-sided oxidation technology of crystal silicon chip high-temperature dry according to claim 1 is characterized in that: regulating the interior temperature of oxidation furnace in the step (5) is 700 ~ 750 ℃, and nitrogen flow is 28000 ~ 30000cm
3/ min, the quartz boat or the graphite boat of silicon chip withdraws from from the oxidation boiler tube in 5 ~ 10min after the oxidation being equipped with.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938434A (en) * | 2012-11-14 | 2013-02-20 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Wet oxidation method for preparing silica masks |
| CN103400891A (en) * | 2013-07-08 | 2013-11-20 | 浙江晶科能源有限公司 | Preparation method of SiO2 passivation layer of back passivation battery |
| WO2014139292A1 (en) * | 2013-03-14 | 2014-09-18 | 苏州阿特斯阳光电力科技有限公司 | Method for preparing crystalline silicon solar cell |
| CN106257625A (en) * | 2016-08-19 | 2016-12-28 | 横店集团东磁股份有限公司 | A kind of stack high-temperature annealing process |
| CN109742185A (en) * | 2018-12-20 | 2019-05-10 | 横店集团东磁股份有限公司 | A kind of alternating temperature transformation thermal oxidation technology improving crystal silicon double-side cell small particles |
| CN110073500A (en) * | 2016-11-02 | 2019-07-30 | 株式会社钟化 | Solar battery and its manufacturing method and solar cell module |
| CN110620030A (en) * | 2018-06-19 | 2019-12-27 | 北京北方华创微电子装备有限公司 | Method for passivating silicon wafer and method for obtaining minority carrier lifetime of silicon wafer |
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| CN101447529A (en) * | 2008-12-22 | 2009-06-03 | 上海晶澳太阳能光伏科技有限公司 | Silica generation technology during manufacturing process of selective emitter solar cells |
| CN102154708A (en) * | 2010-12-31 | 2011-08-17 | 常州天合光能有限公司 | Method for growing solar cell film |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102938434A (en) * | 2012-11-14 | 2013-02-20 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Wet oxidation method for preparing silica masks |
| CN102938434B (en) * | 2012-11-14 | 2014-12-10 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Wet oxidation method for preparing silica masks |
| WO2014139292A1 (en) * | 2013-03-14 | 2014-09-18 | 苏州阿特斯阳光电力科技有限公司 | Method for preparing crystalline silicon solar cell |
| CN103400891A (en) * | 2013-07-08 | 2013-11-20 | 浙江晶科能源有限公司 | Preparation method of SiO2 passivation layer of back passivation battery |
| CN106257625A (en) * | 2016-08-19 | 2016-12-28 | 横店集团东磁股份有限公司 | A kind of stack high-temperature annealing process |
| CN106257625B (en) * | 2016-08-19 | 2019-02-05 | 横店集团东磁股份有限公司 | A kind of stack high-temperature annealing process |
| CN110073500A (en) * | 2016-11-02 | 2019-07-30 | 株式会社钟化 | Solar battery and its manufacturing method and solar cell module |
| CN110620030A (en) * | 2018-06-19 | 2019-12-27 | 北京北方华创微电子装备有限公司 | Method for passivating silicon wafer and method for obtaining minority carrier lifetime of silicon wafer |
| CN110620030B (en) * | 2018-06-19 | 2022-07-22 | 北京北方华创微电子装备有限公司 | Method for passivating silicon wafer and method for obtaining minority carrier lifetime of silicon wafer |
| CN109742185A (en) * | 2018-12-20 | 2019-05-10 | 横店集团东磁股份有限公司 | A kind of alternating temperature transformation thermal oxidation technology improving crystal silicon double-side cell small particles |
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Application publication date: 20120704 |