CN102569481A - 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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CN102569481A
CN102569481A CN2012100223829A CN201210022382A CN102569481A CN 102569481 A CN102569481 A CN 102569481A CN 2012100223829 A CN2012100223829 A CN 2012100223829A CN 201210022382 A CN201210022382 A CN 201210022382A CN 102569481 A CN102569481 A CN 102569481A
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silicon
window layer
thin film
band gap
nano
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CN102569481B (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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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 and preparation method thereof with gradient type band gap characteristic
Technical field
The present invention relates to silica-based solar cell preparation technology, particularly a kind of nano-silicon Window layer and preparation method thereof with gradient type band gap characteristic.
Background technology
Solar cell is solving one of increasingly serious environmental problem and effective way of energy resource supply problem.Because silicon materials are in the extensive use of semicon industry, and people have the understanding that is perfectly clear to the various characteristics of silicon materials.Therefore; Silica-based solar cell occupies important status in all solar cells; Wherein relevant with amorphous silicon solar cell 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 be the amorphous silicon/microcrystalline silicon tandem solar cell on basis, have the favor that very big space enjoys photovoltaic industry circle because of producing in the realization large tracts of land that reduces cost with the amorphous silicon.Different according to the difference of the backing material that adopts and sedimentary sequence; Amorphous silicon film solar battery can be divided into two big types: the first kind is the p-i-n type with transparent substrates such as glass, and its structure is electrode before glass substrate/electrically conducting transparent/amorphous silicon pin knot/electrically conducting transparent back electrode/metal electrode; Second type 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 is meant ITO, SnO2 and ZnO etc., and metal electrode is meant Ag and Al etc.
P type doped layer is as Window layer, forms the built-in potential of solar cell with n type doped layer.Basic demand to p type Window layer is to have 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 the battery basis, so p type Window layer is very crucial for the amorphous silica-based solar cell.If consider from the angle of optics merely; The band gap of p type Window layer is wide more good more; And for the amorphous silicon solar cell of reality, also need consider the coupling between Window layer band gap and the intrinsic layer band gap, like 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 the intrinsic layer band gap will cause the compound increase of interface (p/i) charge carrier between the two, influence the fill factor, curve factor and the open circuit voltage of solar cell, and finally influence 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 Calculation shows, it is compound that the magnetic tape trailer attitude causes is restriction amorphous silicon solar cell V OcMost important factor, the maximum V that obtains through the difference of calculating 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, near above-mentioned calculated value, wherein 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 type Window layer have obtained extensive studies and application.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 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, then be easy to cause the bombardment damage at interface, in n-i-p type amorphous silicon solar cell, cause damage to the i/p interface, reduce the performance of solar cell.
Can find out that from top analysis p type nano-silicon (nc-Si:H) must solve two problems as the Window layer of amorphous silicon solar cell: the 1) damage that causes of the high-energy particle bombardment in the high glow power deposition process; 2) broad-band gap Window layer and than 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 solved two above-mentioned problems effectively.
Summary of the invention
The objective of the invention is to 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, and is easy to implement.
Technical scheme of the present invention:
A kind of nano-silicon Window layer with gradient type band gap characteristic; It is the p type nano-silicon Window layer that on substrate, is superimposed with the pending sample surfaces deposition of metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I successively with gradient type band gap characteristic; Superpose successively by silicon thin film P1, silicon thin film P2 and silicon thin film P3 and to constitute; 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 0.01-0.5eV, and band gap width is 1.8-2.5eV.
A kind of said preparation method with nano-silicon Window layer of gradient type band gap characteristic may further comprise the steps:
The pending sample that 1) will on substrate, be superimposed with metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I is successively put into the high vacuum depositing device; Pending sample surfaces temperature is a room temperature-300 ℃, and the base vacuum degree is not less than 10 -5Pa feeds reacting gas, and reacting gas pressure is 0.5-5Torr, is 0.01-0.1W/cm in glow power density 2Aura depositing silicon film P1 under the condition;
2) with glow power density from 0.01-0.1W/cm 2Increase to 0.1-0.5W/cm gradually 2, aura depositing silicon film P2;
3) be 0.5-5W/cm in glow power density 2Aura depositing silicon film P3 under the condition.
Said depositing device is plasma enhanced chemical vapor deposition PECVD, microwave plasma CVD or the electron cyclotron resonance chemical vapor deposition of 13.56MHz-100MHz.
Said reacting gas comprises: source gas is silanes SiH 4, Si 2H 6Or Si 3H 8Diluent gas is H 2, He or Ar; Impurity gas is BF 3, B 2H 6Or B (CH 3) 3Foreign atom is 0.5-5% with the silicon atom ratio; Diluent gas is 50-500 with the ratio of the flow of source gas: 1.
A kind of said application with nano-silicon Window layer of gradient type band gap characteristic is used 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 that has substrate S, metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I successively; At a certain definite process conditions deposit p type nano-silicon Window layer P, and then preceding electrode T2 of deposit transparent conduction and metal gate electrode M1, a complete amorphous silicon-based film solar cell so just formed.
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 that has substrate S, metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I successively; At first at the p type silicon thin film P1 of a lower glow power deposit thinner thickness; Power deposition film P2, the deposition of completion Window layer P3 under higher power then gradually at last raise.After this, electrode T2 and metal gate electrode M1 before the deposit transparent conduction so just form a complete amorphous silicon-based film solar cell again.The low-power of initial period can obtain lower band gap on the one hand; Help and intrinsic layer between band-gap; The more important thing is that the particle bombardment effect that lower power brings is also little, it is compound significantly to reduce the interface charge carrier, helps 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 that raises gradually helps forming 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.This method adopts the PECVD deposition technique; Scope through effective control deposition parameter; The particularly variation of glow power; Reach the isoparametric purpose of crystallite dimension, crystallization rate, conductivity, activation energy and band gap width of control material, obtained to have high electricity and led the nano-silicon Window layer thin-film material with broad-band gap.Such Window layer material and preparation method are used for the unijunction amorphous silicon film solar battery, can significantly improve the FF and the Voc of solar cell, thereby improve the photoelectric conversion efficiency of solar cell.
Advantage of the present invention is: when this method is used to prepare 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 reduce the bombardment at solar cell i/p (intrinsic layer/Window layer) interface again effectively; Can also realize the band-gap between intrinsic layer and the 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.The preparation method is simple, easy to implement for this nano-silicon Window layer.
Description of drawings
Fig. 1 is a 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 sketch map of the amorphous silicon-based film battery of nano-silicon Window layer respectively, and wherein (a) (b) is gradient gradual change power for to use firm 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 accompanying drawing and specific embodiment technical scheme of the present invention is carried out detailed explanation.
In following examples; The structure of n-i-p type amorphous silicon-based film solar cell is as shown in Figure 1; At the pending sample surfaces that has substrate S, metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I successively; At first at the p type silicon thin film P1 of a lower glow power deposit thinner thickness, the power deposition film P2 that raises gradually then, last under higher power the deposition of completion Window layer P3.After this, electrode T2 and metal gate electrode M1 before the deposit transparent conduction so just form a complete amorphous silicon-based film solar cell again.The practical implementation method is: the pending sample that will have substrate S, metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I successively places reaction chamber; In reaction chamber, feed silane, hydrogen and borine, carry out glow discharge deposition p type Window layer then.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 kind of preparation method with nano-silicon Window layer of gradient type band gap characteristic may further comprise the steps:
The pending sample that 1) will on substrate, be superimposed with metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I is successively 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 feeds reacting gas, and source gas is silanes SiH in the reacting gas 4Diluent gas is H 2Impurity gas is B 2H 6Foreign atom is 1% with the silicon atom ratio; Diluent gas is 250: 1 with the ratio of the flow of source gas, and reacting gas pressure is 2Torr, is 0.08W/cm in glow power density 2The aura deposit thickness is the silicon thin film P1 of 1.5nm under the condition;
2) with glow power density from 0.08W/cm 2Increase to 0.32W/cm gradually 2, the aura deposit thickness is the silicon thin film P2 of 2nm;
3) be 0.32W/cm in glow power density 2The aura deposit thickness is the silicon thin film P3 of 12nm under the condition.
The nano-silicon Window layer that this has gradient type band gap characteristic is used for the nano-silicon Window layer of n-i-p type amorphous silicon-based film solar cell, the open circuit voltage 0.80V of the n-i-p type amorphous silicon solar cell that obtains, 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 sketch map of the amorphous silicon-based film battery of nano-silicon Window layer respectively, and wherein (a) (b) is gradient gradual change power for to use firm power.Clearly show the gradient type band gap characteristic when adopting gradient power among the figure.
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.Show among the figure: when adopting gradient gradual change power method to prepare the nano-silicon Window layer, the spectral response of corresponding n-i-p type amorphous silicon film solar battery is higher, and spectral region is wideer.
Embodiment 2:
A kind of preparation method with nano-silicon Window layer of gradient type band gap characteristic may further comprise the steps:
The pending sample that 1) will on substrate, be superimposed with metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I is successively 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 feeds reacting gas, and source gas is silanes SiH in the reacting gas 4Diluent gas is H 2Impurity gas is B 2H 6Foreign atom is 1% with the silicon atom ratio; Diluent gas is 250: 1 with the ratio of the flow of source gas, and reacting gas pressure is 2Torr, is 0.08W/cm in glow power density 2The aura deposit thickness is the silicon thin film P1 of 1.5nm under the condition;
2) with glow power density from 0.08W/cm 2Increase to 0.56W/cm gradually 2, the aura deposit thickness is the silicon thin film P2 of 3nm;
3) be 0.56W/cm in glow power density 2The aura deposit thickness is the silicon thin film P3 of 11nm under the condition.
The nano-silicon Window layer that this has gradient type band gap characteristic is used for the nano-silicon Window layer of n-i-p type amorphous silicon-based film solar cell, the open circuit voltage 0.88V of the n-i-p type amorphous silicon solar cell that obtains, 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 at first through deposition parameters such as effective control glow powers; Material is deposited between the phase change zone of amorphous silicon/microcrystal silicon; Make the crystallite dimension in the material be controlled at several nanometer scale, increase the band gap width of material, keep the high conductivity of material through quantum limitation effect.Wide band gap and low activation energy help increasing the internal electric field of battery, and high conductivity helps 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 silica-base film depositing operations such as compatible deposition of amorphous silicon, amorphous silicon germanium and microcrystal silicon, and method simply is convenient to operation and is realized, is suitable for suitability for industrialized production.
The above; Be merely the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, any technical staff who is familiar with the present technique field is in the technical scope that the present invention discloses; The variation that can expect easily or replacement all should be encompassed within 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 (5)

1. nano-silicon Window layer with gradient type band gap characteristic; It is the p type nano-silicon Window layer that on substrate, is superimposed with the pending sample surfaces deposition of metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I successively with gradient type band gap characteristic; It is characterized in that: being superposeed successively by silicon thin film P1, silicon thin film P2 and silicon thin film P3 constitutes; 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 0.01-0.5eV, and band gap width is 1.8-2.5eV.
2. preparation method who has the nano-silicon Window layer of gradient type band gap characteristic according to claim 1 is characterized in that may further comprise the steps:
The pending sample that 1) will on substrate, be superimposed with metal back electrode M, electrically conducting transparent back electrode T1, n type silica-base film N and intrinsic silicon base film I is successively put into the high vacuum depositing device; Pending sample surfaces temperature is a room temperature-300 ℃, and the base vacuum degree is not less than 10 -5Pa feeds reacting gas, and reacting gas pressure is 0.5-5Torr, is 0.01-0.1W/cm in glow power density 2Aura depositing silicon film P1 under the condition;
2) with glow power density from 0.01-0.1W/cm 2Increase to 0.1-0.5W/cm gradually 2, aura depositing silicon film P2;
3) be 0.5-5W/cm in glow power density 2Aura depositing silicon film P3 under the condition.
3. according to the said preparation method with nano-silicon Window layer of gradient type band gap characteristic of claim 2, it is characterized in that: said depositing device is plasma enhanced chemical vapor deposition PECVD, microwave plasma CVD or the electron cyclotron resonance chemical vapor deposition of 13.56MHz-100MHz.
4. according to the said preparation method with nano-silicon Window layer of gradient type band gap characteristic of claim 2, it is characterized in that: said reacting gas comprises: source gas is silanes SiH 4, Si 2H 6Or Si 3H 8Diluent gas is H 2, He or Ar; Impurity gas is BF 3, B 2H 6Or B (CH 3) 3Foreign atom is 0.5-5% with the silicon atom ratio; Diluent gas is 50-500 with the ratio of the flow of source gas: 1.
5. application that has the nano-silicon Window layer of gradient type band gap characteristic according to claim 1 is characterized in that: the nano-silicon Window layer that is used for n-i-p type amorphous silicon-based film solar cell.
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Cited By (6)

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CN103165722A (en) * 2013-03-27 2013-06-19 上海空间电源研究所 Microcrystalline silicon thin film solar cell
CN103346192A (en) * 2013-07-23 2013-10-09 常州天合光能有限公司 Novel heterojunction solar cell
CN103915523A (en) * 2014-04-21 2014-07-09 南开大学 Method for preparing silicon heterojunction solar cell containing composite emission layer
CN103972331A (en) * 2013-02-06 2014-08-06 国际商业机器公司 Buffer layer for high performing and low light degraded solar cells and method for forming same
CN104362183A (en) * 2014-09-23 2015-02-18 南开大学 Silicon carbon window layer film with refractive index gradient characteristics and application
CN106711288A (en) * 2017-01-05 2017-05-24 浙江师范大学 Method for manufacturing nano-crystalline silicon thin-film solar cell

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US7667133B2 (en) * 2003-10-29 2010-02-23 The University Of Toledo Hybrid window layer for photovoltaic cells
CN102110734A (en) * 2011-01-18 2011-06-29 西安交通大学 Nanocrystalline silicon/crystalline silicon heterojunction photovoltaic cell

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US7667133B2 (en) * 2003-10-29 2010-02-23 The University Of Toledo Hybrid window layer for photovoltaic cells
CN102110734A (en) * 2011-01-18 2011-06-29 西安交通大学 Nanocrystalline silicon/crystalline silicon heterojunction photovoltaic cell

Cited By (8)

* Cited by examiner, † Cited by third party
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CN103972331A (en) * 2013-02-06 2014-08-06 国际商业机器公司 Buffer layer for high performing and low light degraded solar cells and method for forming same
CN103165722A (en) * 2013-03-27 2013-06-19 上海空间电源研究所 Microcrystalline silicon thin film solar cell
CN103346192A (en) * 2013-07-23 2013-10-09 常州天合光能有限公司 Novel heterojunction 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
CN103915523A (en) * 2014-04-21 2014-07-09 南开大学 Method for preparing silicon heterojunction solar cell containing composite emission layer
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
CN104362183A (en) * 2014-09-23 2015-02-18 南开大学 Silicon carbon window layer film with refractive index gradient characteristics and application
CN106711288A (en) * 2017-01-05 2017-05-24 浙江师范大学 Method for manufacturing nano-crystalline silicon thin-film solar cell

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