CN102330067A - Quick and uniform preparation method of microcrystalline silicon thin film of flexible substrate - Google Patents
Quick and uniform preparation method of microcrystalline silicon thin film of flexible substrate Download PDFInfo
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- CN102330067A CN102330067A CN201110283647A CN201110283647A CN102330067A CN 102330067 A CN102330067 A CN 102330067A CN 201110283647 A CN201110283647 A CN 201110283647A CN 201110283647 A CN201110283647 A CN 201110283647A CN 102330067 A CN102330067 A CN 102330067A
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- microcrystalline silicon
- silicon film
- flexible substrates
- flexible substrate
- heated filament
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Abstract
The invention provides a quick and uniform preparation method of a microcrystalline silicon thin film of a flexible substrate. The method comprises the following steps: placing a flexible substrate in a vacuum chamber; (2) improving the adhesive force of a coating film by the flexible substrate through cleaning activation of glow plasma; and (3) depositing a microcrystalline silicon film by adopting a hot wire assisted very high frequency plasma enhanced chemical vapor deposition method. The invention realizes preparation of the microcrystalline silicon film with high quality, high deposition speed and good uniformity at low temperature by innovatively adopting the hot wire assisted very high frequency plasma enhanced chemical vapor deposition method; and the stability and efficiency of a battery can be effectively improved when the microcrystalline silicon film is applied to a thin film solar battery. The flexible microcrystalline silicon film solar cell has the remarkable characteristics of high mass ratio power, light mass, bending availability, damage prevention and the like, and has wide application prospect in a stratospheric airship, an unmanned aerial vehicle, a miniature satellite, a deep space exploration satellite, a space power station, land military intelligent equipment and other aspects.
Description
Technical field
The present invention relates to quick, the uniform preparation method of flexible substrates high-quality microcrystalline silicon film, belong to field of surface engineering technique.
Background technology
Development along with the military intelligent equipment in space, near space aircraft, unmanned plane and ground; Its energy supplyystem has proposed many new requirements to solar cell; Like: lightweight, efficient, strong capability of resistance to radiation etc., big area high-efficiency soft thin film solar cell can satisfy the demand well.
The flexible amorphous silicon solar cell that with the polyimide is matrix has become the research focus of spacecraft with solar battery system; Flexible amorphous silicon solar cell is as the low cost high power energy simultaneously; It on stratospheric airship only current option; And will replace single crystal silicon solar cell at some space field, especially in the competition of the space solar power station that scientist is studying and exploring, will occupy critical role.
Although the expected results based on the amorphous silicon film solar battery of polyimide substrate has challenging advantage like this, because the photic decay (SW effect) of amorphous silicon material itself is restricting further developing of it.Microcrystalline silicon film has overcome photic decline problem, and being considered to has one of material of application prospect most.Yet the microcrystalline silicon film preparation method who extensively adopts at present-radio-frequency plasma strengthens chemical vapour deposition (RF-PECVD) and combines the shortcoming of appearance very obvious with the technology of flexible substrate:
First; Because common used materials such as relative glass of polyimide substrate resistance to elevated temperatures and stainless steel are relatively poor; So be typically chosen under the lower temperature with RF-PECVD technology growth microcrystalline silicon film, but the structural integrity of sedimentary microcrystalline silicon film is relatively poor, deathnium density is too high; Cause the electricity conversion of flexible microcrystalline silicon solar cell of preparation also very low, be difficult to satisfy space vehicle the thin film solar cell request for utilization;
The second, in order to remedy the problem of poor structural integrity, adopt big hydrogen flow dilution to obtain lower defect concentration as far as possible, often cause sedimentation rate low excessively, simultaneously, the RF-PECVD technology itself not too is suitable for depositing the crystallization silicon film.
For quality and the preparation efficiency that improves microcrystalline silicon film, at present very high frequency plasma enhancing chemical vapour deposition (VHF-PECVD) and hot-wire chemical gas-phase deposition (HW-CVD) methods of adopting more.But VHF-PECVD can't satisfy the uniformity requirement on the fabric width, and that the film of HW-CVD preparation contains pore quantity is on the high side, and battery efficiency is not high.Therefore, be badly in need of a kind of new preparation method of exploitation, realize the preparation of the microcrystalline silicon film of flexible substrates high quality, high deposition rate, good uniformity at low temperatures.
Summary of the invention
For overcoming low temperature deposit membrane structure integrity difference and the low problem of sedimentation rate in the prior art; The present invention adopts the auxiliary very high frequency plasma of heated filament to strengthen chemical gaseous phase depositing process; Realize the preparation of the microcrystalline silicon film of flexible substrates high quality, high deposition rate, good uniformity at low temperatures; Improve the stability and the efficient of thin film solar cell greatly, reduce the cell preparation cost.
For this reason; The technical scheme that is adopted is: a kind of flexible substrates microcrystalline silicon film is quick, the method for uniform preparation; Adopt the auxiliary very high frequency plasma of heated filament to strengthen chemical gaseous phase depositing process deposition micro crystal silicon film; Reach quick, the uniform preparation of flexible substrates microcrystalline silicon film, concrete performing step is following:
(1) flexible substrates is placed in the vacuum chamber, base vacuum is higher than 10
-5Torr;
(2) said flexible substrates is cleaned the sticking power that the activation raising is coated with rete through glow plasma;
(3) adopt the auxiliary VHF plasma reinforced chemical vapour deposition method deposition micro crystal silicon film of heated filament; Heated filament places between VHF source and the sample table; Heated filament and sample table distance are at 5～30mm, and hot-wire temperature's variation range is set in 1300～2000oC, and said flexible substrates does not have the extra-heated system; Used reactant gases is: silane and hydrogen, reactant gases pressure 40～200Pa; Glow power: 20～60W; Diluted in hydrogen silane concentration SC=([SiH
4]/([SiH
4]+[H
2]))=1～15%; Aura excitation frequency: 40～100MHz.
The present invention is directed to the microcrystalline silicon film poor structural integrity and the low problem of sedimentation rate of low temperature depositing; Strengthen the advantage of chemical vapour deposition (VHF-PECVD) and two technology of hot-wire chemical gas-phase deposition (HW-CVD) in conjunction with very high frequency plasma; Novelty ground adopts the auxiliary very high frequency plasma of heated filament to strengthen chemical gaseous phase depositing process; The reactant gases height is decomposed; Regulate processing parameter, can reach the controllable growth of membrane structure, realize the preparation of the microcrystalline silicon film of flexible substrates high quality, high deposition rate, good uniformity under the low temperature.Be applied to thin film solar cell, can improve stability test and efficient effectively.Flexible microcrystalline silicon solar cell possesses high quality specific power, lightweight, distinguishing feature such as flexible, not fragile, and aspect such as military intelligent equipment has very application prospects on stratospheric airship, unmanned plane, microsatellite, survey of deep space satellite, power station, space and ground.
Process method of the present invention is simple, production cost is low, can on plastic-substrates, realize the fast deposition of high-quality microcrystalline silicon film, is equipped with corresponding flexible substrate winding apparatus, can realize the serialization deposition, substitutes existing microcrystal silicon preparation technology.
Description of drawings
Fig. 1 is a process unit synoptic diagram of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further detailed explanation.
With reference to Fig. 1; A kind of quick, uniform preparation method of flexible substrates microcrystalline silicon film; Adopt the auxiliary very high frequency plasma of heated filament to strengthen chemical gaseous phase depositing process high speed deposition micro crystal silicon film on flexible substrates, the VHF input terminus is similar to condenser coupling radio-frequency plasma CVD system in the depositing system, electrode screening and water flowing cooling; Heated filament 4 is between the VHF power utmost point and sample table 6; Sample table 6 is apart from the extremely about 50mm of VHF power, and the distance of regulating between auxiliary heated filament and the sample table 6 is 5～30mm, preferred 10mm.Flexible substrates is example with the polyimide.
The thick flexible polyimide substrate 5 of 25 μ m is placed on the sample table 6, and the vacuum system of forming with mechanical pump and molecular pump 7 vacuumizes, and makes the Vakuumkammer base vacuum be superior to 10
-5Torr.
Turn off molecular pump, feed hydrogen, hydrogen flowing quantity is 20～60sccm, regulates the vacuum valve opening, and making vacuum degree in vacuum chamber is 100Pa.Open the VHF power supply, select the excitation frequency of 70MHz for use, adjusting power is 20～60W, further can be 30～60W, produces hydrogen plasma activation is effectively cleaned in polyimide substrate 6.
Feed SiH
4(H
2Dilution 20%), flow 5～25sccm, diluted in hydrogen silane concentration SC=([SiH
4]/([SiH
4]+[H
2]))=1～15%, further can be SC=([SiH4]/([SiH4]+[H2]))=1～5%; The quality of regulation under meter makes SiH
4And H
2Total flux is controlled at 100 sccm; Aura excitation frequency: 40～100MHz.Regulate the vacuum valve opening, operating air pressure is changed between 40 ~ 200Pa.Said flexible substrates is in the nature soaking condition, no extra-heated system.Open VHF power supply 2, through being added in the temperature of the direct supply 8 control heated filaments on the heated filament 5, the temperature of heated filament 5 is recorded by infrared thermometer, and temperature is controlled at 1300～2000oC.Operating air pressure can preferred 50～180Pa in this step, the preferred 60～90MHz of aura excitation frequency, and the hot-wire temperature is further at 1500～2000oC.
1 is the adaptation in VHF source 2 among Fig. 1, and 3 for feeding the reactant gases of Vakuumkammer.
Claims (1)
- A flexible substrates microcrystalline silicon film fast, the uniform preparation method; It is characterized in that; Adopt the auxiliary very high frequency plasma of heated filament to strengthen chemical gaseous phase depositing process deposition micro crystal silicon film, reach quick, the uniform preparation of flexible substrates microcrystalline silicon film, concrete performing step is following:(1) flexible substrates is placed in the vacuum chamber, base vacuum is higher than 10 -5Torr;(2) said flexible substrates is cleaned the sticking power that the activation raising is coated with rete through glow plasma;(3) adopt the auxiliary VHF plasma reinforced chemical vapour deposition method deposition micro crystal silicon film of heated filament; Heated filament places between VHF source and the sample table; Heated filament and sample table distance are at 5～30mm, and hot-wire temperature's variation range is set in 1300～2000oC, and said flexible substrates does not have the extra-heated system; Used reactant gases is: silane and hydrogen, reactant gases pressure 40～200Pa; Glow power: 20～60W; Diluted in hydrogen silane concentration SC=([SiH 4]/([SiH 4]+[H 2]))=2～15%; Aura excitation frequency: 40～100MHz.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668104A (en) * | 2012-09-24 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for preparing silicon film by carrying out hot filament chemical vapor deposition with ionic liquid as substrate |
| CN104099585A (en) * | 2013-04-09 | 2014-10-15 | 中国科学院大连化学物理研究所 | Apparatus and method for preparing silicon thin film through combination of plasma-enhanced chemical vapor deposition, hot wire chemical vapor deposition and bias technology |
| CN108928479A (en) * | 2018-06-28 | 2018-12-04 | 山东浩坤安全技术咨询有限公司 | A kind of rotor wing unmanned aerial vehicle with solar recharging |
| CN115466939A (en) * | 2022-10-10 | 2022-12-13 | 中国科学院上海微***与信息技术研究所 | Light modulation chemical vapor deposition device and method for modulating film growth temperature by using same |
| CN116864580A (en) * | 2023-09-05 | 2023-10-10 | 眉山琏升光伏科技有限公司 | Process and equipment for preparing microcrystalline silicon film of solar cell |
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| CN1438358A (en) * | 2003-02-13 | 2003-08-27 | 南开大学 | Low-wst technology for quickly growing silicon-base film |
| CN101000867A (en) * | 2006-01-14 | 2007-07-18 | 清华大学 | Manufacturing method of silicon wire |
| CN101257056A (en) * | 2008-04-07 | 2008-09-03 | 南开大学 | Flexible substrate silicon based thin film solar battery |
| US20100326520A1 (en) * | 2009-06-29 | 2010-12-30 | Auria Solar Co., Ltd. | Thin film solar cell and manufacturing method thereof |
| EP2302697A1 (en) * | 2009-09-23 | 2011-03-30 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Solar cell and its production process |
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2011
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Patent Citations (5)
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| CN1438358A (en) * | 2003-02-13 | 2003-08-27 | 南开大学 | Low-wst technology for quickly growing silicon-base film |
| CN101000867A (en) * | 2006-01-14 | 2007-07-18 | 清华大学 | Manufacturing method of silicon wire |
| CN101257056A (en) * | 2008-04-07 | 2008-09-03 | 南开大学 | Flexible substrate silicon based thin film solar battery |
| US20100326520A1 (en) * | 2009-06-29 | 2010-12-30 | Auria Solar Co., Ltd. | Thin film solar cell and manufacturing method thereof |
| EP2302697A1 (en) * | 2009-09-23 | 2011-03-30 | Ecole Polytechnique Fédérale de Lausanne (EPFL) | Solar cell and its production process |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668104A (en) * | 2012-09-24 | 2014-03-26 | 中国科学院大连化学物理研究所 | Method for preparing silicon film by carrying out hot filament chemical vapor deposition with ionic liquid as substrate |
| CN103668104B (en) * | 2012-09-24 | 2016-05-25 | 中国科学院大连化学物理研究所 | Prepare the method for silicon thin film with the hot-wire chemical gas-phase deposition that ionic liquid is made substrate |
| CN104099585A (en) * | 2013-04-09 | 2014-10-15 | 中国科学院大连化学物理研究所 | Apparatus and method for preparing silicon thin film through combination of plasma-enhanced chemical vapor deposition, hot wire chemical vapor deposition and bias technology |
| CN108928479A (en) * | 2018-06-28 | 2018-12-04 | 山东浩坤安全技术咨询有限公司 | A kind of rotor wing unmanned aerial vehicle with solar recharging |
| CN115466939A (en) * | 2022-10-10 | 2022-12-13 | 中国科学院上海微***与信息技术研究所 | Light modulation chemical vapor deposition device and method for modulating film growth temperature by using same |
| CN116864580A (en) * | 2023-09-05 | 2023-10-10 | 眉山琏升光伏科技有限公司 | Process and equipment for preparing microcrystalline silicon film of solar cell |
| CN116864580B (en) * | 2023-09-05 | 2023-12-01 | 眉山琏升光伏科技有限公司 | Process and equipment for preparing microcrystalline silicon film of solar cell |
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Application publication date: 20120125 |