CN102544243A - Intermediate zone material of amorphous silicon film and preparation method thereof - Google Patents
Intermediate zone material of amorphous silicon film and preparation method thereof Download PDFInfo
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- CN102544243A CN102544243A CN2012100888165A CN201210088816A CN102544243A CN 102544243 A CN102544243 A CN 102544243A CN 2012100888165 A CN2012100888165 A CN 2012100888165A CN 201210088816 A CN201210088816 A CN 201210088816A CN 102544243 A CN102544243 A CN 102544243A
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Abstract
The invention discloses a preparation method for an intermediate zone material of an amorphous silicon film and the intermediate zone material of the amorphous silicon film prepared by the method. The preparation method comprises the following steps of selecting materials of a substrate and conducting pre-treatment of the substrate; growing a high-concentration-doped amorphous silicon film on the surface of the pre-treated substrate; and annealing the amorphous silicon film completing growth. The preparation method uses film growth equipment of magnetic control sputtering devices, chemical vapor deposition device and the like, and achieves high concentration even doping of impurities in amorphous silicon on the substrate capable of growing films such as crystalline silicon, quartz, glass and stainless steel by controlling growth conditions, so that the good intermediate zone material of the amorphous silicon film is formed.
Description
Technical field
The invention belongs to new forms of energy photovoltaic technology field, be specifically related to carrying material in the middle of the amorphous silicon membrane of preparation method and the preparation of this method of carrying material in the middle of a kind of amorphous silicon membrane that is used for solar cell.
Background technology
Solar cell is considered to utilize one of effective and efficient manner of this clean energy resource of solar energy.In order more effectively and more cleanly to utilize solar energy, all the time, low-cost and high efficiency all is solar battery technology power of development and target.And for silicon solar cell, with low cost because the silicon materials own resources are abundant, use silicon to come manufacturing solar cells always to be one of main path of manufacturing solar cells.Yet, no matter be to be the crystal silicon solar batteries of material with the crystalline silicon, be the thin-film solar cells of absorbing material still with amorphous silicon, polysilicon membrane, all can not satisfy the requirement that cost is low, efficient is high simultaneously.Therefore, charged pool, hot carrier battery, middle band solar cell etc. can solve high efficiency and the low afoul third generation solar cell of cost is current Development Trend in the middle of the lamination.
For common double-junction solar battery, can not be absorbed less than the photon of its energy bandgaps.This part photon can see through semi-conducting material, causes the loss of energy.And middle band solar cell just can utilize this a part of photon, improves the utilance of battery for sunlight.Middle band solar cell is to utilize technological means such as doping, quantum dot, magnetron sputtering, dilution gold conjugate in the forbidden band of semi-conducting material, to introduce new energy level, thereby feasible photon less than semiconductor gap also can be absorbed by battery.The solar cell that adopts this method to make can effectively improve the short circuit current of battery when not changing open circuit voltage, thereby improves the conversion efficiency of battery.
In order to form the material of the middle band of impurity solar cell, a very important aspect is exactly can be with in the middle of will in the forbidden band, forming.And can be with in the middle of forming, then need in silicon materials, mix gets into the impurity that surpasses its solid solubility far away.The impurity least concentration of band was called the Mott limit in the middle of this can form.With Titanium is example in silicon, and Titanium can form deep energy level in silicon, when titanium concentration reaches its Mott limit in silicon, and just 5 * 10
19Cm
-3When above, the mutual crossover of its impurity energy level can be with in the middle of forming.Yet owing to thermally equilibrated reason, many traditional technology are difficult to make impurity concentration enough high, so that can form impurity band between the impurity energy level.Have only the nonequilibrium technique of employing to improve the doping content of deep-level impurity element in silicon materials, band solar cell material in the middle of could obtaining.
In addition, the research of band solar cell is confined to crystalline material mostly in the middle of the impurity, seldom relates to thin-film material.And cheap like this for amorphous silicon membrane, the simple material of technology did not relate to especially.For the band solar cell of centre, its theoretic peak efficiency, along with crystalline silicon to the increase of thin film silicon material band gap and tangible increase is arranged.Under the illuminate condition for a sun, the highest 31% the battery efficiency that can reach of band solar cell in the middle of the monocrystalline silicon, the band solar cell then can reach about 41% in the middle of the amorphous silicon membrane.Therefore, if be with solar cell material in the middle of preparing amorphous silicon membrane, it will become a kind of very promising material.
Summary of the invention
The technical problem that (one) will solve
The main purpose of patent of the present invention is to provide carrying material in the middle of the amorphous silicon membrane of preparation method and the preparation of this method of carrying material in the middle of a kind of amorphous silicon membrane that is used for solar cell, to improve the photoelectric conversion efficiency of solar cell.
(2) technical scheme
For solving the problems of the technologies described above, the present invention proposes the preparation method of the middle carrying material of a kind of amorphous silicon membrane, and this method may further comprise the steps: select the material of substrate and substrate is carried out preliminary treatment; Amorphous silicon membrane at pretreated substrate surface growth high-concentration dopant; Amorphous silicon membrane to growth is accomplished is annealed.
According to preferred implementation of the present invention, the material of said substrate is monocrystalline silicon, quartz, glass or stainless steel.
According to preferred implementation of the present invention, in the step of the amorphous silicon membrane of said growth high-concentration dopant, dopant material is made up of the element that can in the forbidden band of silicon, form energy level.
According to preferred implementation of the present invention, said dopant material is titanium, aluminium, indium, magnesium or sulphur.
According to preferred implementation of the present invention, the step of the amorphous silicon membrane of said growth high-concentration dopant is to carry out not being higher than under 400 ℃ the temperature.
According to preferred implementation of the present invention, the step of the amorphous silicon membrane of said growth high-concentration dopant is in the atmosphere of hydrogen, to carry out.
According to preferred implementation of the present invention, the step that the amorphous silicon membrane of growth completion is annealed is in the atmosphere of nitrogen or hydrogen, to carry out.
According to preferred implementation of the present invention, the step that the amorphous silicon membrane that growth is accomplished is annealed is to carry out not being higher than under 400 ℃ the temperature.
The present invention also proposes the middle carrying material of a kind of amorphous silicon membrane, and this material is got by method for preparing of the present invention, and its absorptivity near infrared band is more than 50%.
(3) beneficial effect
The present invention utilizes magnetron sputtering apparatus; Film growth apparatus such as chemical vapor depsotition equipment; On crystal silicon, quartz, glass, stainless steel etc. much can the substrates of growing film; Through the control to growth conditions, the high concentration of realization impurity in amorphous silicon evenly mixed, thereby forms the middle carrying material of good amorphous silicon membrane.Therefore this material can effectively improve the absorption of amorphous silicon battery to the near infrared band sunlight owing in the forbidden band of silicon, formed intermediate level, improves the efficient of non-crystal silicon solar cell.Technology of the present invention is simple, and is lower to the requirement of substrate and growing environment, adopts the film of this prepared, can realize large-area growth, and this helps reducing the cost of unit are.
Description of drawings
Fig. 1 is according on substrate, the grow sketch map of carrying material in the middle of the amorphous silicon membrane of embodiments of the invention;
Fig. 2 is the SIMS figure according to carrying material in the middle of the amorphous silicon membrane of embodiments of the invention cosputtering growth;
Fig. 3 is according to the amorphous silicon cosputtering film of embodiments of the invention growth and does not mix the absorption spectra comparison diagram of the amorphous silicon thin-film materials of Titanium near infrared band.
Embodiment
For making the object of the invention, technical scheme and advantage clearer,, and, the present invention is done further detailed description with reference to accompanying drawing below in conjunction with specific embodiment.
Fig. 1 is according on substrate, the grow sketch map of carrying material in the middle of the amorphous silicon membrane of embodiments of the invention.See also structure shown in Figure 1, the preparation method who is used for the middle carrying material of amorphous silicon membrane of solar cell of the present invention may further comprise the steps:
Step 1: select the material of substrate and substrate is carried out preliminary treatment;
Step 2: at the amorphous silicon membrane of pretreated substrate surface growth high-concentration dopant;
Step 3: the amorphous silicon membrane to growth is accomplished is annealed.
The following specifically describes above-mentioned three steps.
In the step 1, the material of substrate can be chosen as crystalline silicon, also can be glass, quartz, stainless steel etc., as long as it meets the film growth requirement, all can be used as the material of this substrate that is.In the present embodiment, select for use crystalline silicon as backing material, its crystal orientation can be (100) or (111).
For backing material, need carry out preliminary treatment, for example its surface is cleaned.In this enforcement, adopt silicon substrate, pre-treatment step comprises with the concentrated sulfuric acid boiled 5 minutes, cleaned with deionized water then, used the hydrofluoric acid rinsing again 30 seconds.If adopt quartz as substrate, then need carry out degreasing treatment to it, for example boil successively and wash with acetone, ethanol, use the deionized water wash clean then.
In the step 2, through backing material being put into the material grower, be controlled under certain condition realizing that the high concentration of impurity in amorphous silicon evenly mix, thereby forming the amorphous silicon membrane of high-concentration dopant on the surface of substrate.Described dopant material can be elements such as titanium, aluminium, indium, magnesium and sulphur, but the present invention is not limited to this, and dopant material can be made up of any element that can form energy level in the forbidden band of silicon.High-concentration dopant of the present invention is meant that doping content is higher than this material forms middle band in silicon least concentration.
In the present embodiment, the substrate that cleans up is put into growth apparatus, growth apparatus can be a magnetron sputtering apparatus, also can be Chemical Vapor Deposition Equipment.In growth course, in growth apparatus, feed hydrogen, thin-film material is grown in the atmosphere of hydrogen.
According to the present invention, the temperature of film growth can not be above 400 ℃.And growing environment parameters such as power through regulating magnetron sputtering or source of the gas concentration make dopant material in amorphous silicon thin-film materials, reach highly doped.In the present embodiment, utilize silicon target and titanium target and magnetron sputtering apparatus to carry out magnetron sputtering, and the control growing temperature is at 300 ℃, regulates that the sputtering power of silicon target material and titanium target is respectively 100W and 3W in the magnetron sputtering apparatus, growth time is 2 hours.
Fig. 2 is the SIMS figure according to carrying material in the middle of the amorphous silicon membrane of present embodiment cosputtering growth.As shown in Figure 2, resulting thin-film material is that titanium concentration is greater than 10
19Cm
-3Titanium and the thin-film material of amorphous silicon cosputtering, and the concentration of titanium is evenly distributed in film.
In the step 3, the thin-film material that growth is accomplished is annealed.According to the present invention, annealing temperature is no more than 400 ℃.In this embodiment, control annealing temperature is crossed at 400 ℃, and in the atmosphere of nitrogen, anneals, and annealing time is about half an hour.
Measurement shows, utilizes the middle carrying material of amorphous silicon membrane of method preparation of the present invention at the absorptivity of near infrared band certain enhancing to be arranged.
Fig. 3 is according to the amorphous silicon cosputtering thin-film material of embodiments of the invention growth and does not mix the absorption spectra comparison diagram of the amorphous silicon thin-film materials of Titanium near infrared band.As shown in Figure 3; In the above-described embodiments; The titanium, the amorphous silicon cosputtering that on silicon substrate, utilize the mode of magnetron sputtering to grow have obtained amorphous silicon thin-film materials, and its absorptivity near infrared band is significantly improved compared to the amorphous silicon thin-film materials that does not have the doping metals titanium.In Fig. 3, round dot is the absorptivity of the amorphous silicon thin-film materials of present embodiment, and side point is for similarity condition time but there is not the absorptivity of the amorphous silicon thin-film materials of Doped with Titanium.Visible from Fig. 3, the near infrared band at 1100nm-1700nm of amorphous silicon thin-film materials of the present invention, its optical absorptivity are all more than 50%, and than the amorphous silicon thin-film materials that does not have Doped with Titanium, its absorptivity is significantly improved.
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of the middle carrying material of amorphous silicon membrane is characterized in that, may further comprise the steps:
Select the material of substrate and substrate is carried out preliminary treatment;
Amorphous silicon membrane at pretreated substrate surface growth high-concentration dopant;
Amorphous silicon membrane to growth is accomplished is annealed.
2. the preparation method of carrying material is characterized in that in the middle of the amorphous silicon membrane as claimed in claim 1, and said high-concentration dopant is meant that doping content is higher than this material forms middle band in silicon least concentration.。
3. the preparation method of carrying material is characterized in that the material of said substrate is monocrystalline silicon, quartz, glass or stainless steel in the middle of the amorphous silicon membrane as claimed in claim 2.
4. the preparation method of carrying material is characterized in that in the step of the amorphous silicon membrane of said growth high-concentration dopant, dopant material is made up of the element that can in the forbidden band of silicon, form energy level in the middle of the amorphous silicon membrane as claimed in claim 2.
5. the preparation method of carrying material is characterized in that said dopant material is titanium, aluminium, indium, magnesium or sulphur in the middle of the amorphous silicon membrane as claimed in claim 4.
6. the preparation method of carrying material is characterized in that in the middle of the amorphous silicon membrane as claimed in claim 2, and the step of the amorphous silicon membrane of said growth high-concentration dopant is to carry out not being higher than under 400 ℃ the temperature.
7. the preparation method of carrying material is characterized in that the step of the amorphous silicon membrane of said growth high-concentration dopant is in the atmosphere of hydrogen, to carry out in the middle of the amorphous silicon membrane as claimed in claim 6.
8. the preparation method of carrying material is characterized in that in the middle of the amorphous silicon membrane as claimed in claim 2, and the step that the amorphous silicon membrane of growth completion is annealed is in the atmosphere of nitrogen or hydrogen, to carry out.
9. the preparation method of carrying material is characterized in that in the middle of the amorphous silicon membrane as claimed in claim 8, and the step that the amorphous silicon membrane that growth is accomplished is annealed is to carry out not being higher than under 400 ℃ the temperature.
10. the middle carrying material of amorphous silicon membrane is characterized in that, this material is prepared by each the described preparation method among the claim 1-9 and gets, and its absorptivity near infrared band is more than 50%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891191A (en) * | 2012-09-29 | 2013-01-23 | 中国科学院半导体研究所 | Amorphous silicon intermediate zone solar battery and preparation method thereof |
Citations (1)
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| CN102191563A (en) * | 2011-04-22 | 2011-09-21 | 中国科学院半导体研究所 | Preparation method of codoped silicon-base impurity intermediate belt material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102191563A (en) * | 2011-04-22 | 2011-09-21 | 中国科学院半导体研究所 | Preparation method of codoped silicon-base impurity intermediate belt material |
Non-Patent Citations (3)
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| G.GONZALEZ-DIAZ ETC.: "《Intermediate band mobility in heavily titanium-doped silicon layers》", 《SOLAR ENERGY MATERIALS&SOLAR CELLS》 * |
| 赵志明 等: "《基于磁控溅射技术沉积光伏电池用硅基薄膜材料的研究》", 《西安理工大学学报》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102891191A (en) * | 2012-09-29 | 2013-01-23 | 中国科学院半导体研究所 | Amorphous silicon intermediate zone solar battery and preparation method thereof |
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Application publication date: 20120704 |