CN102569481B - Nano silicon window layer with gradient band gap characteristic and preparation method thereof - Google Patents

Nano silicon window layer with gradient band gap characteristic and preparation method thereof Download PDF

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CN102569481B
CN102569481B CN201210022382.9A CN201210022382A CN102569481B CN 102569481 B CN102569481 B CN 102569481B CN 201210022382 A CN201210022382 A CN 201210022382A CN 102569481 B CN102569481 B CN 102569481B
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silicon
window layer
thin film
band gap
nano
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CN102569481A (en
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侯国付
倪牮
马峻
刘飞连
张晓丹
赵颖
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Nankai University
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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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • 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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    • 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

Abstract

The invention relates to a nano silicon window layer with the gradient band gap characteristic, which is formed by depositing on the surface of a sample to be processed, wherein the surface of the sample to be processed is sequentially stacked with a metal back electrode M, a transparent conductive back electrode T1, an n-type Si-based thin film N and an intrinsic Si-based thin film I. The nano silicon window layer is formed by sequentially stacking a silicon thin film P1, a silicon thin film P2 and a silicon thin film P3. A preparation method of the nano silicon window layer comprises the following steps: depositing the p-type silicon thin film P1 with small thickness under a low glow power; then gradually raising the power and depositing the thin film P2; and finally, and completing the window layer P3 under a high power. The nano silicon window layer has the advantages that when the nano silicon window layer is applied to the window layer of an n-i-p-type silicon-based thin film solar cell, high electric conductance and wide band gap can be acquired, the bombardment of a solar cell i/p interface can be effectively reduced, the band gap matching between an intrinsic layer and the window layer can be implemented and the filling factor, the open-circuit voltage and the spectral response of the solar cell are obviously improved, so that the silicon-based thin film solar cell with high photoelectric conversion efficiency is obtained.

Description

A kind of nano-silicon Window layer with gradient type band gap characteristic and preparation method thereof
Technical field
The present invention relates to silica-based solar cell preparation technology, particularly a kind of nano-silicon Window layer with gradient type band gap characteristic and preparation method thereof.
Background technology
Solar cell is solving one of increasingly serious environmental problem and effective way of energy resource supply problem.Due to the extensive use of silicon materials at semicon industry, and people have the understanding being perfectly clear to the various characteristics of silicon materials.Therefore, silica-based solar cell occupies very important status in all solar cells, wherein the solar cell relevant to amorphous silicon comprises amorphous silicon-based film solar cell (containing microcrystal silicon and amorphous silicon germanium etc.), and the HIT type heterojunction solar cell of amorphous silicon/monocrystalline silicon formation.
In silicon-based thin film solar cell, amorphous silicon (a-Si:H) thin film solar cell, particularly take amorphous silicon as basic amorphous silicon/microcrystalline silicon tandem solar cell, because realizing large area and produce and to there is the favor that very large space enjoys photovoltaic industry circle reducing costs.According to the difference of backing material and the difference of sedimentary sequence that adopt, amorphous silicon film solar battery can be divided into two large classes: the first kind is the p-i-n type with transparent substrates such as glass, and its structure is electrode/amorphous silicon pin knot/electrically conducting transparent back electrode/metal electrode before glass substrate/electrically conducting transparent; Equations of The Second Kind is the n-i-p type with opaque substrates such as stainless steels, at the bottom of its structure is stainless steel lining/metal electrode/electrically conducting transparent back electrode/amorphous silicon pin knot/electrically conducting transparent before electrode/metal gate electrode.Wherein, nesa coating TCO refers to ITO, SnO2 and ZnO etc., and metal electrode refers to Ag and Al etc.
P-type doped layer, as Window layer, forms the built-in potential of solar cell together with N-shaped doped layer.To the basic demand of p-type Window layer, be to there is high conductivity, low activation energy and broad-band gap, wherein high conductivity and low activation energy can strengthen internal electric field and reduce Window layer and transparency conductive electrode between contact resistance, broad-band gap can make more light incide absorbed layer in battery basis, so p-type Window layer is very crucial for amorphous silica-based solar cell.If considered from the angle of optics merely, the band gap of p-type Window layer is more wide better, and for actual amorphous silicon solar cell, also need to consider mating between Window layer band gap and intrinsic layer band gap, as amorphous silicon intrinsic layer band gap～1.8eV, amorphous silicon germanium intrinsic layer 1.4-1.6eV, microcrystalline silicon intrinsic layer 1.2eV.Mismatch between Window layer band gap and intrinsic layer band gap will cause the compound increase of interface (p/i) charge carrier between the two, affect fill factor, curve factor and the open circuit voltage of solar cell, and finally affect photoelectric conversion efficiency of the solar battery.
Another major issue is the open circuit voltage V of amorphous silicon solar cell occlose with the property relationship of p-type Window layer.Theoretical calculating show, it is compound that magnetic tape trailer state causes is restriction amorphous silicon solar cell V ocmost important factor, the maximum V obtaining by calculating the difference of intrinsic layer electronics and hole quasi fermi level ocvalue be 1.0 ± 0.1V.And in fact, the V of solar cell ocnot only relevant with intrinsic layer, also closely related with the relation of Window layer.Experimentally can access V at present octhe amorphous silicon solar cell that surpasses 1.0V, approached above-mentioned calculated value, wherein very important effect has also been played in the optimization aspect Window layer, referring to: Xianbo Liao, Wenhui Du, Xiesen Yang, et al, Journal of Non-Crystalline Solids, Vol.352,2006,1841-1846.
In amorphous silicon film solar battery, a-SiC:H, the p-type of μ c-SiC:H and nc-Si:H or N-shaped Window layer have obtained studying widely and applying.Because a-SiC:H and μ c-SiC:H can cause the pollution of intrinsic layer carbon, so have the desirable Window layer selection that the p-type nano-silicon (p-nc-Si:H) of broad-band gap and low activation energy is considered to amorphous silicon solar cell, wherein broad-band gap derives from the quantum limitation effect with nano-scale silicon crystal grain.In order to obtain this nc-Si:H Window layer material, generally need high power, highly diluted and the high comparatively harsh experiment conditions such as deposition pressure.If glow power is on the low side, be difficult to obtain broad-band gap; If glow power is very high, be easy to cause the bombardment damage at interface, in n-i-p type amorphous silicon solar cell, cause the damage to i/p interface, reduce the performance of solar cell.
As can be seen from the above analysis, p-type nano-silicon (nc-Si:H) must solve two problems as the Window layer of amorphous silicon solar cell: the damage that 1) high-energy particle bombardment in high glow power deposition process causes; 2) broad-band gap Window layer and compared with the band-gap between the intrinsic layer of low band gaps and band gap transition.For this reason, the present invention proposes a kind of nano-silicon Window layer with gradient type band gap characteristic and preparation method thereof, has effectively solved two above-mentioned problems.
Summary of the invention
The object of the invention is for above-mentioned technical Analysis, a kind of nano-silicon Window layer with gradient type band gap characteristic and preparation method thereof is provided, this nano-silicon Window layer can significantly improve n-i-p type silicon-based thin film solar cell photoelectric conversion efficiency, and its preparation method is simple, easy to implement.
Technical scheme of the present invention:
A kind of nano-silicon Window layer with gradient type band gap characteristic, on substrate, to be superimposed with successively metal back electrode M, electrically conducting transparent back electrode T1, the p-type nano-silicon Window layer with gradient type band gap characteristic of the pending sample surfaces deposition of N-shaped silica-base film N and intrinsic silicon base film I, by silicon thin film P1, silicon thin film P2 and the silicon thin film P3 formation that superposes successively, silicon thin film P1 wherein, the thickness of silicon thin film P2 and silicon thin film P3 is respectively 0.5-2nm, 1-3nm and 5-30nm, the gross thickness of whole nano-silicon Window layer is 10-50nm, crystallite dimension is 1-10nm, conductivity is 0.00001-5S/cm, activation energy is 0.01-0.5eV, band gap width is 1.8-2.5eV.
Described in there is the preparation method of the nano-silicon Window layer of gradient type band gap characteristic, comprise the following steps:
1) the pending sample that is superimposed with successively metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I on substrate is put into high vacuum depositing device, pending sample surfaces temperature is room temperature-300 ℃, and base vacuum degree is not less than 10 -5pa, passes into reacting gas, and reacting gas pressure is 0.5-5Torr, in glow power density, is 0.01-0.1W/cm 2aura depositing silicon film P1 under condition;
2) by glow power density from 0.01-0.1W/cm 2increase to gradually 0.1-0.5W/cm 2, aura depositing silicon film P2;
3) in glow power density, be 0.5-5W/cm 2aura depositing silicon film P3 under condition.
Described depositing device is plasma enhanced chemical vapor deposition PECVD, microwave plasma CVD or the electron cyclotron resonance chemical vapor deposition of 13.56MHz-100MHz.
Described reacting gas comprises: source gas is silanes SiH 4, Si 2h 6or Si 3h 8; Diluent gas is H 2, He or Ar; Impurity gas is BF 3, B 2h 6or B (CH 3) 3; Foreign atom is 0.5-5% with silicon atom ratio; Diluent gas is 50-500 with the ratio of the flow of source gas: 1.
Described in there is the application of the nano-silicon Window layer of gradient type band gap characteristic, for the nano-silicon Window layer of n-i-p type amorphous silicon-based film solar cell.
Analysis on Mechanism of the present invention:
In n-i-p type amorphous silicon-based film solar cell, conventional p-type Window layer preparation method is, at the pending sample surfaces successively with substrate S, metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I, under a certain definite process conditions, deposit p-type nano-silicon Window layer P, and then the front electrode T2 of deposit transparent conduction and metal gate electrode M1, so just form a complete amorphous silicon-based film solar cell.
The nano-silicon Window layer preparation method that the present invention's proposition has gradient type band gap characteristic is, at the pending sample surfaces successively with substrate S, metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I, first under a lower glow power, deposit the p-type silicon thin film P1 of thinner thickness, then the power deposition film P2 that raises gradually finally completes the deposition of Window layer P3 under higher power.After this, the more front electrode T2 of deposit transparent conduction and metal gate electrode M1, a complete amorphous silicon-based film solar cell so just formed.The low-power of initial period can obtain lower band gap on the one hand, be conducive to and intrinsic layer between band-gap, the more important thing is that the particle bombardment effect that lower power brings is also little, can significantly reduce interface charge carrier compound, be conducive to the improvement of Voc and FF.The high power of final stage can obtain the nano-silicon of broad-band gap, and the middle power raising is gradually conducive to form the bandgap structure of gradient gradual change.
The present invention proposes to have nano-silicon Window layer of gradient type band gap characteristic and preparation method thereof, takes into account the processing compatibility of considering with existing amorphous silicon-based film solar cell.The method adopts PECVD deposition technique, by the scope of effective control deposition parameter, the particularly variation of glow power, reach the isoparametric object of crystallite dimension, crystallization rate, conductivity, activation energy and band gap width of controlling material, obtained and there is high electricity and lead the nano-silicon Window layer thin-film material with broad-band gap.Such Window layer material and preparation method, for unijunction amorphous silicon film solar battery, can significantly improve FF and the Voc of solar cell, thereby improve the photoelectric conversion efficiency of solar cell.
Advantage of the present invention is: by the method during for the preparation of the Window layer of n-i-p type silicon-based thin film solar cell, can either obtain high electricity leads and broad-band gap, can effectively reduce the bombardment at solar cell i/p (intrinsic layer/Window layer) interface again, can also realize the band-gap between intrinsic layer and Window layer, thereby can significantly improve fill factor, curve factor, open circuit voltage and the shortwave spectral response of solar cell, thereby obtain the silicon-based thin film solar cell of high-photoelectric transformation efficiency.Preparation method is simple, easy to implement for this nano-silicon Window layer.
Accompanying drawing explanation
Fig. 1 is n-i-p type amorphous silicon film solar battery structural representation, and wherein p-type nano-silicon Window layer adopts the preparation of gradient gradual change power.
Fig. 2 is for to adopt firm power and gradient gradual change power to prepare the band structure schematic diagram of the amorphous silicon-based film battery of nano-silicon Window layer respectively, and wherein (a), for firm power, (b) is gradient gradual change power.
Fig. 3 is for to adopt firm power and gradient gradual change power to prepare the quantum efficiency QE curve of the n-i-p type amorphous silicon silicon-film solar-cell of nano-silicon Window layer respectively.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical solutions according to the invention are described in detail.
In following examples, the structure of n-i-p type amorphous silicon-based film solar cell as shown in Figure 1, at the pending sample surfaces successively with substrate S, metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I, first under a lower glow power, deposit the p-type silicon thin film P1 of thinner thickness, then the power deposition film P2 that raises gradually finally completes the deposition of Window layer P3 under higher power.After this, the more front electrode T2 of deposit transparent conduction and metal gate electrode M1, a complete amorphous silicon-based film solar cell so just formed.Specific implementation method is: the pending sample successively with substrate S, metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I is placed in to reaction chamber, in reaction chamber, pass into silane, hydrogen and borine, then carry out glow discharge deposition p-type Window layer.According to the difference of glow power, prepared one group of n-i-p type amorphous silicon solar cell with different p-type Window layer.
Introduce two embodiment of the present invention below.
Embodiment 1:
A preparation method with the nano-silicon Window layer of gradient type band gap characteristic, comprises the following steps:
1) the pending sample that is superimposed with successively metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I on substrate is put into the plasma enhanced chemical gas phase PECVD depositing device of 13.56MHz-100MHz, pending sample surfaces temperature is 150 ℃, base vacuum degree 2 * 10 -4pa, passes into reacting gas, and in reacting gas, source gas is silanes SiH 4; Diluent gas is H 2; Impurity gas is B 2h 6; Foreign atom is 1% with silicon atom ratio; Diluent gas is 250: 1 with the ratio of the flow of source gas, and reacting gas pressure is 2Torr, in glow power density, is 0.08W/cm 2the silicon thin film P1 that under condition, aura deposit thickness is 1.5nm;
2) by glow power density from 0.08W/cm 2increase to gradually 0.32W/cm 2, the silicon thin film P2 that aura deposit thickness is 2nm;
3) in glow power density, be 0.32W/cm 2the silicon thin film P3 that under condition, aura deposit thickness is 12nm.
This has the nano-silicon Window layer of gradient type band gap characteristic, for the nano-silicon Window layer of n-i-p type amorphous silicon-based film solar cell, and the open circuit voltage 0.80V of the n-i-p type amorphous silicon solar cell obtaining, short-circuit current density 13.86mA/cm 2, fill factor, curve factor 61%, photoelectric conversion efficiency 6.76%.
Fig. 2 is for to adopt firm power and gradient gradual change power to prepare the band structure schematic diagram of the amorphous silicon-based film battery of nano-silicon Window layer respectively, and wherein (a), for firm power, (b) is gradient gradual change power.In figure, clearly show the gradient type band gap characteristic while adopting gradient power.
Fig. 3 is for to adopt firm power and gradient gradual change power to prepare the quantum efficiency QE curve of the n-i-p type amorphous silicon film solar battery of nano-silicon Window layer respectively.In figure, show: when adopting gradient gradual change power method to prepare nano-silicon Window layer, the spectral response of corresponding n-i-p type amorphous silicon film solar battery is higher, and spectral region is wider.
Embodiment 2:
A preparation method with the nano-silicon Window layer of gradient type band gap characteristic, comprises the following steps:
1) the pending sample that is superimposed with successively metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I on substrate is put into the plasma enhanced chemical gas phase PECVD depositing device of 13.56MHz-100MHz, pending sample surfaces temperature is 150 ℃, base vacuum degree 2 * 10 -4pa, passes into reacting gas, and in reacting gas, source gas is silanes SiH 4; Diluent gas is H 2; Impurity gas is B 2h 6; Foreign atom is 1% with silicon atom ratio; Diluent gas is 250: 1 with the ratio of the flow of source gas, and reacting gas pressure is 2Torr, in glow power density, is 0.08W/cm 2the silicon thin film P1 that under condition, aura deposit thickness is 1.5nm;
2) by glow power density from 0.08W/cm 2increase to gradually 0.56W/cm 2, the silicon thin film P2 that aura deposit thickness is 3nm;
3) in glow power density, be 0.56W/cm 2the silicon thin film P3 that under condition, aura deposit thickness is 11nm.
This has the nano-silicon Window layer of gradient type band gap characteristic, for the nano-silicon Window layer of n-i-p type amorphous silicon-based film solar cell, and the open circuit voltage 0.88V of the n-i-p type amorphous silicon solar cell obtaining, short-circuit current density 13.52mA/cm 2, fill factor, curve factor 63%, photoelectric conversion efficiency 7.5%.
It is worth noting, the present invention is first by effectively controlling the deposition parameters such as glow power, can make deposition of material between the phase change zone of amorphous silicon/microcrystal silicon, make the crystallite dimension in material be controlled at several nanometer scale, by quantum limitation effect, increase the band gap width of material, keep the high conductivity of material.Wide band gap and low activation energy are conducive to increase the internal electric field of battery, and high conductivity is conducive to the reduction of series resistance, thereby make the V of battery ocall obtain raising in various degree with FF, thereby improved efficiency of solar cell.
In addition, the present invention obtains nano-silicon on the basis of the silica-base film depositing operations such as compatible deposition of amorphous silicon, amorphous silicon germanium and microcrystal silicon, and the simple convenient operation of method is realized, and is suitable for suitability for industrialized production.
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, is anyly familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection range of claim.

Claims (3)

1. a preparation method with the nano-silicon Window layer of gradient type band gap characteristic, described nano-silicon Window layer is superposeed and forms successively by silicon thin film P1, silicon thin film P2 and silicon thin film P3, wherein the thickness of silicon thin film P1, silicon thin film P2 and silicon thin film P3 is respectively 0.5-2nm, 1-3nm and 5-30nm, the gross thickness of whole nano-silicon Window layer is that 10-50nm, crystallite dimension are that 1-10nm, conductivity are that 0.00001-5S/cm, activation energy are that 0.01-0.5eV, band gap width are 1.8-2.5eV, it is characterized in that comprising the following steps:
1) the pending sample that is superimposed with successively metal back electrode M, electrically conducting transparent back electrode T1, N-shaped silica-base film N and intrinsic silicon base film I on substrate is put into high vacuum depositing device, pending sample surfaces temperature is room temperature-300 ℃, and base vacuum degree is not less than 10 -5pa, passes into reacting gas, and reacting gas pressure is 0.5-5Torr, in glow power density, is 0.01-0.1W/cm 2aura depositing silicon film P1 under condition;
2) by glow power density from 0.01-0.1W/cm 2increase to gradually 0.1-0.5W/cm 2, aura depositing silicon film P2;
3) in glow power density, be 0.5-5W/cm 2aura depositing silicon film P3 under condition.
2. the preparation method according to claim 1 with the nano-silicon Window layer of gradient type band gap characteristic, is characterized in that: plasma enhanced chemical vapor deposition PECVD equipment, microwave plasma CVD equipment or electron cyclotron resonance chemical vapor deposition equipment that described high vacuum depositing device is 13.56MHz-100MHz.
3. the preparation method according to claim 1 with the nano-silicon Window layer of gradient type band gap characteristic, is characterized in that: described reacting gas comprises: source gas is silanes SiH 4, Si 2h 6or Si 3h 8; Diluent gas is H 2, He or Ar; Impurity gas is BF 3, B 2h 6or B (CH 3) 3; Foreign atom is 0.5-5% with silicon atom ratio; Diluent gas is 50-500:1 with the ratio of the flow of source gas.
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US20140217408A1 (en) * 2013-02-06 2014-08-07 International Business Machines Corporaton Buffer layer for high performing and low light degraded solar cells
CN103165722A (en) * 2013-03-27 2013-06-19 上海空间电源研究所 Microcrystalline silicon thin film solar cell
CN103346192B (en) * 2013-07-23 2015-09-09 常州天合光能有限公司 A kind of novel heterojunction solar battery
CN103915523B (en) * 2014-04-21 2016-02-10 南开大学 A kind of preparation method containing composed emission layer silicon heterojunction solar battery
CN104362183B (en) * 2014-09-23 2017-02-01 南开大学 Silicon carbon window layer film with refractive index gradient characteristics and application
CN106711288B (en) * 2017-01-05 2018-02-27 浙江师范大学 A kind of preparation method of Nano silicon-crystal thin film solar cell

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