CN104851940A - Method for preparing silicon nanowire arrays on flexible substrate - Google Patents
Method for preparing silicon nanowire arrays on flexible substrate Download PDFInfo
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- CN104851940A CN104851940A CN201410781080.9A CN201410781080A CN104851940A CN 104851940 A CN104851940 A CN 104851940A CN 201410781080 A CN201410781080 A CN 201410781080A CN 104851940 A CN104851940 A CN 104851940A
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- flexible substrate
- stainless steel
- steel flexible
- hydrogen
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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
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Abstract
The invention relates to the technical field of film solar cells in new energy and particularly relates to a method for preparing silicon nanowire arrays on a stainless steel flexible substrate. First, a layer of tin-doppedindium oxide (ITO) film is settled on the stainless steel flexible substrate by adopting a magnetic control sputtering method. Second, the stainless steel flexible substrate obtained in the first step is transferred to a reactive cavity and the ITO film is subjected to etching treatment by utilizing hydrogen plasma etching method, and nanometer particles of indium are obtained. Third, growth of silicon nanowires (including i-type, p-type and n-type silicon nanowires) on the stainless steel flexible substrate obtained in the second step is allowed by adopting plasma enhanced chemical vapor deposition (PECVD) technology. According to the invention, by adopting a plasma enhanced chemical vapor deposition system, the treatment process is simple and practical and is low in temperature and low in energy consumption. Besides, the growth of silicon nanowires and the deposition of the silicon film are compatible to each other, so that further steps for making silicon film devices are very convenient.
Description
Technical field
The present invention relates to the technical field of thin film solar cell in new forms of energy, particularly relate to a kind of method preparing silicon nanowire array on flexible substrates.
Background technology
Fossil energy burning produces a large amount of waste gas, and severe contamination, the biological environment destroying the earth make the living environment of the mankind more and more worsen, and the natural environment that the protection mankind depend on for existence and natural resources become the global problem be jointly concerned about the world today.The development strategy that development is efficient, clean energy technology is world energy sources.2006, China's " Renewable Energy Law " formally promulgated, country increases the working dynamics of development new forms of energy, released every relevant favorable policy and supported development, exploitation regenerative resource energetically.In " 12 " development plan, further the development of regenerative resource particularly solar energy is classified as the field that emphasis is first developed.From world wide, photovoltaic generation has started to enter batch production and sizable application stage, but also has certain limitation from the large-scale application of solar energy.This is mainly not high enough from the photoelectric conversion efficiency of battery and battery cost is high, finds cheap, that material that is efficient solar battery is various countries' research all the time key areas.
Due to the raw material rich reserves of silicon, the solar cell of preparation has higher conversion efficiency, material non-toxic, can not pollute environment, thus becomes a kind of more satisfactory solar cell material.Silicon solar cell mainly comprises crystal silicon solar energy battery and thin film silicon solar cell.Crystal silicon solar energy battery conversion efficiency is higher, and technology is also ripe.But crystalline silicon material cost is higher, need in preparation process to consume a large amount of materials and energy.The amorphous silicon film solar battery main target always enjoying people to pay close attention to is exactly to reduce battery cost, and people start to attempt utilizing cheap polysilicon, even metallurgical grade silicon to make solar cell in recent years.But the key issue of these batteries is, electron diffusion length is wherein too short and photo-generated carrier cannot be transported to smoothly space charge region, thus fails effectively to be collected by electrode.For addressing this problem, seminar of California Inst Tech USA proposes to adopt the silicon nanowires solar cell of radial p-n junction that orthogonalization is carried out in the direction of light absorption and carrier transport, utilize longer nano wire axially to carry out absorb photons, and can contribute to diametrically collecting photo-generated carrier.Theory calculate shows, electron diffusion length is that the radial silicon nanowires efficiency of solar cell of 100nm can reach 11%, and far above 1.5% of slab construction, therefore this new ideas battery structure has very large potentiality in making lower cost materials solar cell.In addition, this seminar adopts electrochemical erosion method to make large hole nano line on crystalline silicon, tentatively achieve radial silicon nanowire array solar cell, with the radial solar cell of this fabrication techniques compared with classic flat-plate crystal-silicon solar cell, efficiency just declines slightly, people can utilize this technology on low-quality silicon materials, make radial silicon nanowires solar cell, thus reduce the material cost of battery.On the other hand, the silicon nanowires of this radial structure have also been obtained Preliminary Applications on amorphous silicon film battery.The light absorption that amorphous silicon nanowire is strong and effective anti-reflection effect are by the reduction of the raising and cost that impel silicon film solar batteries efficiency further.As can be seen here, silicon nanowires is expected for the prospect of photovoltaic device very much.
Summary of the invention
The object of the invention is to provide a kind of method preparing silicon nanowire array on flexible substrates; the method can improve the photoelectric properties of silicon nanowires; there is preparation technology simple and easy to do; cost is lower; the advantage such as be produced on a large scale, and can be widely used in multiple industry fields such as solar cell.
The object of the invention is to be achieved through the following technical solutions.
The present invention relates to a kind of method preparing silicon nanowire array on flexible substrates, steps of the method are:
1) in stainless steel flexible substrate, magnetically controlled sputter method is adopted to deposit one deck tin-doped indium oxide (ITO) film;
2) by step 1) the stainless steel flexible substrate that obtains is transferred to reaction chamber, utilizes hydrogen gas plasma lithographic method carry out etching processing to ITO and obtain the nano particle of indium metal;
3) in step 2) using plasma assistant chemical vapor deposition (PECVD) technology growth silicon nanowires (comprising i type, p-type and N-shaped silicon nanowires) in the stainless steel flexible substrate that obtains.
Above-mentioned steps 1) in the magnetically controlled sputter method concrete grammar that deposits one deck tin-doped indium oxide (ITO) film be:
First before the deposition, by stainless steel flexible substrate wipe oil, to boil with deionized water and boil and ultrasonic cleaning process drying; Cleaned stainless steel flexible substrate is put in magnetron sputtering reaction chamber, makes the background vacuum of the chamber of magnetron sputtering be better than 1.0 × 10
-3pa, makes the temperature of stainless steel flexible substrate be 100 DEG C, now, stops vacuumizing, and start magnetron sputtering, the magnetron sputtering time is 1min, and the thickness of deposition tin-doped indium oxide (ITO) film is 10nm; Wherein, magnetron sputtering target used is the ITO target of 99.9% purity (can be higher);
Above-mentioned step 2) in utilize hydrogen gas plasma lithographic method to the method that ITO etches to be:
Transfer in PECVD chamber by the stainless steel flexible substrate being coated with ITO, chamber background vacuum is 1 × 10
-3-2 × 10
-3pa, the temperature of the stainless steel flexible substrate in chamber is 400 DEG C, now, stops vacuumizing, and passes into hydrogen, and hydrogen flowing quantity is 6 × 10
-3m
3/ h, chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, hydrogen plasma etching processing duration is 10min, obtains the indium metal particle of nano-scale magnitude;
Above-mentioned steps 3) in stainless steel flexible substrate the method for using plasma assistant chemical vapor deposition (PECVD) technology growth silicon nanowires be:
After obtaining indium metal nano particle on flexible substrates, PECVD reaction chamber is vacuumized, makes its vacuum degree be 1 × 10
-3-2 × 10
-3pa, then pass into silane and hydrogen toward chamber or pass into silane, hydrogen and impurity gas, wherein, the impurity gas of N-shaped silicon nanowires is phosphine, the impurity gas of p-type silicon nanowires is borine, build-up of luminance carries out Silicon nanowire growth, and growth conditions is as follows: stainless steel flexible substrate temperature is 400 DEG C, and silane flow rate is 3.6 × 10
-4m
3/ h, hydrogen flowing quantity is 3.6 × 10
-3m
3/ h, reaction chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, sedimentation time is 20-40min.
In above-mentioned steps, if depositing n-type silicon nanowires, wherein the flow control of impurity gas phosphine is 3.6 × 10
-4m
3/ h; If depositing p-type silicon nanowires, wherein the flow of impurity gas borine is 3.6 × 10
-4m
3/ h.
Beneficial effect
1, this method preparing silicon nanowire array on flexible substrates of the present invention's proposition, using plasma assistant chemical vapor deposition system, processing procedure is simple and easy to do, low temperature low energy consumption, and the deposition of the growth of silicon nanowires and silicon thin film is compatible, very convenient further making silicon thin film device.
2, be different from the golden catalysis extensively adopted at present, adopt indium metal to carry out catalysis, the silicon nanowires grown out can be made to avoid the pollution of deep-level impurity, and photoelectric properties are more excellent, thus in the middle of solar cell, have good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope image of the intrinsic silicon nano wire that embodiment 1 deposits in stainless steel flexible substrate;
Fig. 2 is the scanning electron microscope image of the doped silicon nano wire that embodiment 2 deposits in stainless steel flexible substrate;
Wherein scanning electron microscopy is JOEL instrument, and multiplication factor is 10000 times, and voltage is 15kv.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1: the method for deposition intrinsic silicon nanowires
1) in the stainless steel flexible substrate of 2cm × 2cm × 0.5mm, adopt magnetically controlled sputter method to deposit thick tin-doped indium oxide (ITO) film of 10nm;
2) by step 1) the stainless steel flexible substrate that obtains is transferred to reaction chamber, utilizes hydrogen gas plasma lithographic method carry out etching processing to ITO and obtain the nano particle of indium metal;
3) in step 2) using plasma assistant chemical vapor deposition (PECVD) technology growth i type silicon nanowires in the stainless steel flexible substrate that obtains.
Above-mentioned steps 1) in the magnetically controlled sputter method concrete grammar that deposits one deck tin-doped indium oxide (ITO) film be:
First before the deposition, by stainless steel flexible substrate wipe oil, to boil with deionized water and boil and ultrasonic cleaning process drying; Cleaned stainless steel flexible substrate is put in magnetron sputtering reaction chamber, makes the background vacuum of the chamber of magnetron sputtering be better than 1.0 × 10
-3pa, makes the temperature of stainless steel flexible substrate be 100 DEG C, now, stops vacuumizing, and start magnetron sputtering, the magnetron sputtering time is 1min, and the thickness of deposition tin-doped indium oxide (ITO) film is 10nm; Wherein, magnetron sputtering target used is the ITO target of 99.9% purity;
Above-mentioned step 2) in utilize hydrogen gas plasma lithographic method to the method that ITO etches to be:
Transfer in PECVD chamber by the stainless steel flexible substrate being coated with ITO, chamber background vacuum is 1 × 10
-3-2 × 10
-3pa, the temperature of the stainless steel flexible substrate in chamber is 400 DEG C, now, stops vacuumizing, and passes into hydrogen, and hydrogen flowing quantity is 6 × 10
-3m
3/ h, chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, hydrogen plasma etching processing duration is 10min, obtains the indium metal particle of nano-scale magnitude;
Above-mentioned steps 3) in stainless steel flexible substrate the method for using plasma assistant chemical vapor deposition (PECVD) technology growth silicon nanowires be:
After obtaining indium metal nano particle on flexible substrates, PECVD reaction chamber is vacuumized, makes its vacuum degree be 1 × 10
-3, then pass into silane and hydrogen toward chamber, build-up of luminance carries out Silicon nanowire growth, and growth conditions is as follows: stainless steel flexible substrate temperature is 400 DEG C, and silane flow rate is 3.6 × 10
-4m
3/ h, hydrogen flowing quantity is 3.6 × 10
-3m
3/ h, reaction chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, sedimentation time is 40min, obtains i type silicon nanowires, and as shown in Figure 1, from figure, the diameter of silicon nanowires is 100nm-200nm to its scanning electron microscope image, and length is 3 μm-5 μm.
Embodiment 2: the method for dopant deposition silicon nanowires
1) in 2cm × 2cm × 0.5mm stainless steel flexible substrate, adopt magnetically controlled sputter method to deposit thick tin-doped indium oxide (ITO) film of 10nm;
2) by step 1) the stainless steel flexible substrate that obtains is transferred to reaction chamber, utilizes hydrogen gas plasma lithographic method carry out etching processing to ITO and obtain the nano particle of indium metal;
3) in step 2) using plasma assistant chemical vapor deposition (PECVD) technology growth N-shaped silicon nanowires in the stainless steel flexible substrate that obtains.
Above-mentioned steps 1) in the magnetically controlled sputter method concrete grammar that deposits one deck tin-doped indium oxide (ITO) film be:
First before the deposition, by stainless steel flexible substrate wipe oil, to boil with deionized water and boil and ultrasonic cleaning process drying; Cleaned stainless steel flexible substrate is put in magnetron sputtering reaction chamber, makes the background vacuum of the chamber of magnetron sputtering be better than 1.0 × 10
-3pa, makes the temperature of stainless steel flexible substrate be 100 DEG C, now, stops vacuumizing, and start magnetron sputtering, the magnetron sputtering time is 1min, and the thickness of deposition tin-doped indium oxide (ITO) film is 10nm; Wherein, magnetron sputtering target used is the ITO target of 99.9% purity;
Above-mentioned step 2) in utilize hydrogen gas plasma lithographic method to the method that ITO etches to be:
Transfer in PECVD chamber by the stainless steel flexible substrate being coated with ITO, chamber background vacuum is 1 × 10
-3pa, the temperature of the stainless steel flexible substrate in chamber is 400 DEG C, now, stops vacuumizing, and passes into hydrogen, and hydrogen flowing quantity is 6 × 10
-3m
3/ h, chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, hydrogen plasma etching processing duration is 10min, obtains the indium metal particle of nano-scale magnitude;
Above-mentioned steps 3) in stainless steel flexible substrate the method for using plasma assistant chemical vapor deposition (PECVD) technology growth silicon nanowires be:
After obtaining indium metal nano particle on flexible substrates, PECVD reaction chamber is vacuumized, makes its vacuum degree be 1 × 10
-3pa, then passes into silane, hydrogen and impurity gas toward chamber, and build-up of luminance carries out Silicon nanowire growth, and growth conditions is as follows: stainless steel flexible substrate temperature is 400 DEG C, and silane flow rate is 3.6 × 10
-4m
3/ h, hydrogen flowing quantity is 3.6 × 10
-3m
3/ h, reaction chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, sedimentation time is 20min.Wherein the flow of impurity gas phosphine is 3.6 × 10
-4m
3/ h, obtains N-shaped doped silicon nano wire, and the flow of impurity gas borine is 3.6 × 10
-4m
3/ h, obtains p-type doped silicon nano wire, and as shown in Figure 2, from figure, the diameter of silicon nanowires is 100nm-200nm to its scanning electron microscope image, length 1 μm-3 μm.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; all do within principle of the present invention and spirit any amendment, equivalent to replace and improvement etc., be all just included within protection scope of the present invention.
Claims (4)
1. prepare a method for silicon nanowire array on flexible substrates, it is characterized in that steps of the method are:
1) in stainless steel flexible substrate, magnetically controlled sputter method is adopted to deposit one deck tin-doped indium oxide film;
2) by step 1) the stainless steel flexible substrate that obtains is transferred to reaction chamber, utilizes hydrogen gas plasma lithographic method carry out etching processing to tin-doped indium oxide film and obtain the nano particle of indium metal;
3) in step 2) using plasma assistant chemical vapor deposition technology growth silicon nanowires in the stainless steel flexible substrate that obtains;
Above-mentioned steps 1) in the magnetically controlled sputter method concrete grammar that deposits one deck tin-doped indium oxide film be:
First before the deposition, by stainless steel flexible substrate wipe oil, to boil with deionized water and boil and ultrasonic cleaning process drying; Cleaned stainless steel flexible substrate is put in magnetron sputtering reaction chamber, makes the background vacuum of magnetron sputtering chamber be better than 1.0 × 10
-3pa, the temperature of stainless steel flexible substrate is 100 DEG C, and now, start magnetron sputtering, the magnetron sputtering time is 1min, and the thickness of deposition tin-doped indium oxide film is 10nm; Wherein, magnetron sputtering target used is the ITO target of 99.9% purity;
Above-mentioned step 2) in utilize hydrogen gas plasma lithographic method to the method that ITO etches to be:
Transfer in assistant chemical vapor deposition chamber by the stainless steel flexible substrate being coated with ITO, chamber background vacuum is 1 × 10
-3pa, the temperature of the stainless steel flexible substrate in chamber is 400 DEG C, now, passes into hydrogen, and hydrogen flowing quantity is 6 × 10
-3m
3/ h, chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, hydrogen plasma etching processing duration is 10min, obtains the indium metal particle of nano-scale magnitude;
Above-mentioned steps 3) in stainless steel flexible substrate the method for using plasma assistant chemical vapor deposition technology growth silicon nanowires be:
After stainless steel flexible substrate obtains indium metal nano particle, plasma assistant chemical vapor deposition reaction chamber vacuumizes, and makes its vacuum degree be 1 × 10
-3-2 × 10
-3pa, then passes into reacting gas toward chamber, and build-up of luminance carries out Silicon nanowire growth, and growth conditions is as follows: stainless steel flexible substrate temperature is 400 DEG C, and silane flow rate is 3.6 × 10
-4m
3/ h, hydrogen flowing quantity is 3.6 × 10
-3m
3/ h, reaction chamber pressure is 200Pa, the glow power 500mW/cm of radio-frequency power supply
2, sedimentation time is 20-40min.
2. a kind of method preparing silicon nanowire array on flexible substrates according to claim 1, is characterized in that: during preparation i type silicon nanowires, the reacting gas passed into is silane and hydrogen.
3. a kind of method preparing silicon nanowire array on flexible substrates according to claim 1, is characterized in that: when preparing N-shaped silicon nanowires, and the reacting gas passed into is silane, hydrogen and phosphine, and the flow control of phosphine is 3.6 × 10
-4m
3/ h.
4. a kind of method preparing silicon nanowire array on flexible substrates according to claim 1, is characterized in that: during preparation p-type silicon nanowires, the reacting gas passed into is silane, hydrogen and borine, and the flow control of borine is 3.6 × 10
-4m
3/ h.
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| CN105568223A (en) * | 2016-03-02 | 2016-05-11 | 电子科技大学 | Preparation method for silicon nanowire |
| CN106409653A (en) * | 2016-03-31 | 2017-02-15 | 兰州大学 | Silicon nanowire array preparation method |
| CN106587068A (en) * | 2016-12-12 | 2017-04-26 | 陕西科技大学 | Method for preparing single Si nanowire by virtue of tin dioxide |
| CN106637127A (en) * | 2016-12-12 | 2017-05-10 | 陕西科技大学 | Method for preparing Si multi-nanowire array by using tin dioxide |
| CN107768640A (en) * | 2017-10-19 | 2018-03-06 | 中国科学院过程工程研究所 | A kind of crystallization/amorphous silicon carbon nanocoils and its preparation method and application |
| CN109850843A (en) * | 2019-03-14 | 2019-06-07 | 南京大学 | A kind of hanging nano wire manipulator batch preparation |
| CN111112642A (en) * | 2019-12-18 | 2020-05-08 | 宁波大学 | Method for preparing germanium nanowires |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568223A (en) * | 2016-03-02 | 2016-05-11 | 电子科技大学 | Preparation method for silicon nanowire |
| CN106409653A (en) * | 2016-03-31 | 2017-02-15 | 兰州大学 | Silicon nanowire array preparation method |
| CN106409653B (en) * | 2016-03-31 | 2021-04-09 | 兰州大学 | Preparation method of silicon nanowire array |
| CN106587068A (en) * | 2016-12-12 | 2017-04-26 | 陕西科技大学 | Method for preparing single Si nanowire by virtue of tin dioxide |
| CN106637127A (en) * | 2016-12-12 | 2017-05-10 | 陕西科技大学 | Method for preparing Si multi-nanowire array by using tin dioxide |
| CN107768640A (en) * | 2017-10-19 | 2018-03-06 | 中国科学院过程工程研究所 | A kind of crystallization/amorphous silicon carbon nanocoils and its preparation method and application |
| CN107768640B (en) * | 2017-10-19 | 2020-09-08 | 中国科学院过程工程研究所 | Crystalline/amorphous silicon-carbon nanowire and preparation method and application thereof |
| CN109850843A (en) * | 2019-03-14 | 2019-06-07 | 南京大学 | A kind of hanging nano wire manipulator batch preparation |
| CN109850843B (en) * | 2019-03-14 | 2021-01-15 | 南京大学 | Batch preparation method of suspended nanowire manipulator |
| CN111112642A (en) * | 2019-12-18 | 2020-05-08 | 宁波大学 | Method for preparing germanium nanowires |
| CN111112642B (en) * | 2019-12-18 | 2022-09-27 | 宁波大学 | Method for preparing germanium nanowires |
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Application publication date: 20150819 |