CN101510566B - Wide bandgap N type nanometer silicon material for silicon film solar battery and preparation method - Google Patents
Wide bandgap N type nanometer silicon material for silicon film solar battery and preparation method Download PDFInfo
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- CN101510566B CN101510566B CN2009100681539A CN200910068153A CN101510566B CN 101510566 B CN101510566 B CN 101510566B CN 2009100681539 A CN2009100681539 A CN 2009100681539A CN 200910068153 A CN200910068153 A CN 200910068153A CN 101510566 B CN101510566 B CN 101510566B
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Abstract
The invention discloses a wide-bandgap N-type nano silicon material used for a silicon thin film solar battery and a preparation method thereof; the material is a phosphor-doped or arsenic-doped N-type wide-bandgap nano silicon thin film; the preparation method comprises the steps: firstly, samples to be treated are put into a high-vacuum deposition system and the corresponding material is prepared by utilizing a plasma-enhanced chemical vapor deposition method through effectively controlling deposition parameters such as the glow discharge power and the silane concentration. In the preparation method, the structural features and photoelectric properties of the material can be effectively controlled through the optimization of the parameters such as the discharge power and the silane concentration; and the nano-effect caused by the reduction of the grain sizes is utilized to obtain the N-type nano silicon with high conductivity and wide bandgap. The wide-bandgap N-type nano silicon material has the advantages that: when being used as the doped layer of the amorphous silicon solar battery, the wide-bandgap N-type nano silicon can significantly enhance the build-in electric field of the battery and greatly increase open-circuit voltage, thus obtaining the amorphous silicon solar battery with high photoelectric transformation efficiency.
Description
Technical field
The present invention relates to silicon-based thin film solar cell preparation technology, belong to the technical field of thin film solar cell in the new forms of energy.
Background technology
In the silicon-based thin film solar cell, non-crystalline silicon (a-Si:H) thin film solar cell particularly has the favor that very big space enjoys photovoltaic industry circle based on the amorphous silicon/microcrystalline silicon tandem solar cell of non-crystalline silicon because of producing in the realization large tracts of land that reduces cost.In the silicon-based thin film solar cell of P-I-N structure, the N layer forms the built-in potential of solar cell with the P layer; And in amorphous/crystallite stacked solar cell, cascade solar cell, top battery N layer also constitutes with the microcrystal silicon P layer of end battery wears composite junction (TunnelRecombination Junction then, TRJ), play crucial effects for improving battery open circuit voltage (Voc) acquisition efficient solar battery.How to obtain having high V
OcNon-crystalline silicon top battery and microcrystal silicon at the bottom of battery, for improving unijunction non-crystalline silicon or microcrystal silicon battery, or the photoelectric transformation efficiency of amorphous silicon/microcrystalline silicon tandem battery is most important.
Usually the method that improves silicon thin-film battery be adopt that high electricity is led, the p type doped layer of broad-band gap and the optimization of intrinsic layer realizes.Such as, adopt p type nano-silicon can make the V of amorphous silicon battery as Window layer
OcReach 1.042V (Xianbo Liao, WenhuiDu, Xiesen Yang, et al, Journal of Non-Crystalline Solids, Vol.352,2006,1841-1846).In fact, also extremely important as the effect of a utmost point N type doped layer of solar cell, but at present about N type doped layer to silicon-film solar-cell V
OcThe research of influence is less.
Generally be applied in the silicon thin film single junction cell as doped layer traditionally with N type non-crystalline silicon.Big (the E of the band gap width of N type non-crystalline silicon
Opt～1.75eV), but the also big (E of activation energy
a～0.4eV), the difference E of band gap and activation energy
Opt-E
a～1.35eV; Though though N type microcrystal silicon can reach very low activation energy (E
a＜0.1eV), but the also less (E of its band gap width
Opt～1.3eV), so the difference E of band gap and activation energy
Opt-E
a～1.3eV is suitable substantially with the difference of N type non-crystalline silicon.Therefore, when adopting N type non-crystalline silicon or N type microcrystal silicon as the N layer material of non-crystalline silicon or microcrystal silicon single junction cell, the V of respective battery
OcThere is not tangible difference: the V of non-crystalline silicon single junction cell
OcAt 0.9eV, the V of microcrystal silicon single junction cell
OcAt 0.5eV.And in non-crystalline silicon/microcrystal silicon (perhaps non-crystalline silicon/non-crystalline silicon) stacked solar cell, cascade solar cell, the raising that N/P wears the battery performance of becoming a partner then is very crucial.Since N type non-crystalline silicon electricity lead lower, during as top battery N layer and the effect of wearing then between the end battery P layer be not very desirable; Though the introducing of N type microcrystal silicon has effectively solved the problem of wearing then of N/P knot in the laminated cell, because the band gap width of N type microcrystal silicon is less, causes non-crystalline silicon top battery V in the laminated cell
OcOn the low side, thereby limited laminated cell V
OcRaising.
Summary of the invention
The invention provides and a kind ofly can improve silicon-based thin film solar cell V
OcThereby improve broad-band gap nanometer N layer material of battery efficiency and preparation method thereof.
The wide bandgap N type nano silicon material of silicon-film solar-cell of the present invention, be to have substrate G, nesa coating T successively, on the intrinsic silicon film I layer of the pending sample of boron dopen Nano silicon Window layer P and intrinsic silicon base film I sedimentary deposit is arranged, thickness is at 10～50nm, crystallite dimension 5～50nm, crystallization rate 5～50%, dark conductivity 0.001～5S/cm, activation energy 0.01～0.5eV, band gap width 1.8～2.5eV; And sedimentary condition is: electrode distance is 21mm, and the silane concentration scope is increased to 4%, 4.5%, 4.75%, 5%, 5.5%, 15% successively since 3%; The deposition pressure range is from 0.5Torr to 2Torr.
The preparation method of the wide bandgap N type nano silicon material of silicon-film solar-cell may further comprise the steps:
A, will have substrate G, nesa coating T successively, the pending sample of boron dopen Nano silicon Window layer P and intrinsic silicon base film I is put into the high vacuum depositing system, and base vacuum is higher than 10
-5Pa;
B, feeding reacting gas;
C, reacting gas is added power begin aura, deposition obtains required thin-film material.
Described deposition process is the plasma enhanced chemical vapor deposition PECVD of 13.56MHz～100MHz, perhaps microwave CVD, perhaps heated filament CVD, perhaps electron cyclotron resonace CVD;
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 PH
3Or AsH
3
Control glow power and silane concentration, the Nano thin film that feasible deposition obtains is between microcrystal silicon and non-crystalline silicon transition region and close microcrystal silicon one side, and the correlative sediments parameter area is:
Glow power: 10～100W;
Reacting gas pressure: 0.5～2Torr;
Electrode distance is 21mm;
The silane concentration scope is increased to 4%, 4.5%, 4.75%, 5%, 5.5%, 15% successively since 3%;
Pending sample surfaces temperature: 100-200 ℃;
Doping ratio, promptly foreign atom compares with silicon atom: 0.5～5%.
Silicon-based thin film solar cell, for unijunction or tie stacked solar cell, cascade solar cell, described single junction cell structure is a substrate G/ nesa coating T/ boron dopen Nano silicon Window layer P11/ intrinsic silicon base film I1/ phosphorus doping Nano thin film N1/ metal M more; Described many knot stacked solar cell, cascade solar cell structures are substrate G/ nesa coating T/ boron dopen Nano silicon Window layer P1/ intrinsic silicon base film I1/ phosphorus doping Nano thin film N1/ boron doped microcrystalline silicon P2/ intrinsic micro crystal silicon thin film I2/ phosphorus doping N type non-crystalline silicon/metal M, and wherein the used N1 layer film of silicon-based thin film solar cell is aforesaid wide bandgap N type nano silicon material.
The Voc of described amorphous silicon battery is greater than 0.9V, microcrystal silicon battery V
OcGreater than 0.5eV.
Beneficial effect of the present invention is: control the structure and the photoelectric properties thereof of N type doped layer by the deposition parameter of effective control deposition process, reach the high conductivity of doped layer, the basic demand of broad-band gap.This broad-band gap nano-silicon is as the doped layer of amorphous silicon battery, can significantly strengthen the built in field of battery, improve the open-circuit voltage of battery greatly, wear characteristic preferably then, thereby significantly improve the transformation efficiency of unijunction and many knot laminated cells and in many knot laminated cells, also help acquisition.
Description of drawings
Fig. 1 is unijunction P-I-N non-crystalline silicon (or microcrystal silicon) thin-film solar cell structure schematic diagram;
Fig. 2 is double junction non-crystal silicon/microcrystal silicon (or non-crystalline silicon/non-crystalline silicon) stacked solar cell, cascade solar cell structural representation;
The V of unijunction amorphous silicon solar cell when Fig. 3 is N layer difference crystallization rate
OcChange curve with FF.
The specific embodiment
Below in conjunction with the drawings and specific embodiments technical solutions according to the invention are described in detail.
The present invention utilizes the interlinking of deposition micro crystal silicon or amorphous silicon membrane depositing operation deposition, the preparation method of the N type nano silicon material of a kind of compatible microcrystal silicon and microcrystalline silicon film deposition technique is provided, this method adopts the PECVD deposition technique, scope by effective control deposition parameter, reach the crystallite dimension and the crystallization rate of control material, obtained to have the N type Nano thin film material of broad-band gap, resulting N type Nano thin film material has higher relatively electrical conductivity simultaneously.High electricity is led, the silicon Window layer P1 of broad-band gap, intrinsic silicon base film I1, phosphorus doping Nano thin film N1 and metal M.Wherein G is a clear glass; T is nesa coating SnO
2: F; P1 is boron doped P type nanometer Si or other forms of P-type material.Intrinsic layer I1 is a non-crystalline silicon; N1 is described phosphorus doping broad-band gap Nano thin film; Metal M can be Al or Ag.
Amorphous of the present invention/crystalline/micro-crystalline silicon laminated solar battery structure comprises substrate G as shown in Figure 2, nesa coating T, boron dopen Nano silicon Window layer P1, intrinsic film I1, phosphorous doped silicon base film N1, boron doped microcrystalline silicon thin film P2, intrinsic film I2, phosphorous doped silicon base film N2 and metal M.Wherein G is a clear glass; T is SnO
2: the F nesa coating; P1 is boron doped P type nanometer Si or other forms of P-type material.Intrinsic layer I1 is a non-crystalline silicon; N1 is described phosphorus doping broad-band gap Nano thin film; P2 is boron doped P type microcrystal silicon.Intrinsic layer I2 is a microcrystal silicon; N2 is the phosphorus doping amorphous silicon membrane, and metal M can be Al or Ag.
The present invention be directed to the unijunction amorphous silicon solar cell of P-I-N structure or the binode amorphous/crystalline/micro-crystalline silicon laminated solar battery of P-I-N/P-I-N structure, proposed to solve silica-based battery V
OcNovel N type nano silicon material on the low side and preparation method thereof.
According to shown in Figure 1, introduce three embodiment of the present invention below:
Embodiment 1
Comparatively preferred implementation condition is as follows among the present invention: will have substrate G, nesa coating T successively, the pending sample of boron dopen Nano silicon Window layer P and intrinsic silicon base film I places reaction chamber, in reaction chamber, feed silane, hydrogen and phosphine, air pressure in the chamber remains on 0.7Torr, and electrode distance is 21mm.The beginning aura, at first being provided with through the power after optimizing is 10W, regulates silane concentration, scope is increased to 4%, 4.5%, 4.75%, 5%, 5.5%, 15% successively since 3%; Change glow power then, scope is from 10W to 50W; Adjust deposition pressure at last, scope is from 0.5Torr to 2Torr.The control sedimentation time makes the consistency of thickness of the N layer film that obtains under the different silane concentrations in the experimentation.By the relative photo electrical characteristics of test material, obtain having one group of deposition parameter of relatively optimizing of high conductivity and wide bandgap N type material: pressure 1.0Torr, silane concentration 8%, glow power 15W, 200 ℃ of depositing temperatures.The N type nano silicon material performance that obtains like this is: band gap width 2.05eV, electrical conductivity 1S/cm, activation energy 0.02eV.
Embodiment 2
Crystallization rate in Fig. 3 (Xc) the corresponding N type non-crystalline silicon that equals zero is common N type non-crystalline silicon, its electrical conductivity 3 * 10
-4S/cm, band gap width 1.8eV.Adopt the N type doped layer of above-mentioned common N type non-crystalline silicon as the unijunction amorphous silicon battery, the performance parameter of respective battery is: open-circuit voltage 0.89V, fill factor, curve factor 69%, short-circuit current density 13.6mA/cm2, battery conversion efficiency 8.35%.
Embodiment 3
At pressure 1.0Torr, silane concentration 8%, 200 ℃ of N type nano silicon material performances that prepare of glow power 15W and depositing temperature are: band gap width 2.05eV, electrical conductivity 1S/cm, activation energy 0.02eV.When adopting nano silicon material as the N type doped layer of non-crystalline silicon single junction cell, the performance parameter of respective battery is: open-circuit voltage 0.945V, fill factor, curve factor 73%, short-circuit current density 13.7mA/cm2, battery conversion efficiency 9.45%. for the N type non-crystalline silicon among the embodiment 2, the V of battery
OcImprove 0.55V, FF also increases, and battery efficiency improves above 1 percentage point, and effect is remarkable.
It is worth noting, the present invention is at first by effectively controlling deposition parameters such as silane concentration, power, material is deposited between the phase change zone of non-crystalline silicon/microcrystal silicon, control the crystallite dimension in the material that corresponding deposition obtains, increase the band gap width of material, reduce the high conductivity that the material crystallization rate keeps material simultaneously.Wide band gap and low activation energy help increasing the built in field of battery, and high electrical conductivity helps the reduction of series resistance, thereby make the V of battery
OcAll obtain raising in various degree with FF, thereby improved battery efficiency.
In addition, the present invention obtains nano-silicon on the basis of compatible deposition micro crystal silicon and amorphous silicon deposition technology, and method simply is convenient to operation and is realized, is suitable for suitability for industrialized production.
The above; only for the preferable specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art 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 domain of claim.
Claims (5)
1. wide bandgap N type nanometer silicon material for silicon film solar battery, it is characterized in that: have substrate G, nesa coating T successively, on the intrinsic silicon film I layer of the pending sample of boron dopen Nano silicon Window layer P and intrinsic silicon base film I sedimentary deposit is arranged, thickness is at 10～50nm, crystallite dimension 5～50nm, crystallization rate 5～50%, dark conductivity 0.001～5S/cm, activation energy 0.01～0.5eV, band gap width 1.8～2.5eV; And sedimentary condition is: electrode distance is 21mm, and the silane concentration scope is increased to 4%, 4.5%, 4.75%, 5%, 5.5%, 15% successively since 3%; The deposition pressure range is from 0.5Torr to 2Torr.
2. the preparation method of a wide bandgap N type nanometer silicon material for silicon film solar battery is characterized in that may further comprise the steps:
A, will have substrate G, nesa coating T successively, the pending sample of boron dopen Nano silicon Window layer P and intrinsic silicon base film I is put into the high vacuum depositing system, and base vacuum is higher than 10
-5Pa;
B, feeding reacting gas;
C, reacting gas is added power begin aura, deposition obtains required thin-film material;
Described deposition process is the plasma enhanced chemical vapor deposition PECVD of 13.56MHz～100MHz, perhaps microwave CVD, perhaps heated filament CVD, perhaps electron cyclotron resonace CVD;
Described 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 PH
3Or AsH
3
Control glow power and silane concentration, the Nano thin film that feasible deposition obtains is between microcrystal silicon and non-crystalline silicon transition region and close microcrystal silicon one side, and the correlative sediments parameter area is:
Glow power: 10～100W;
Reacting gas pressure: 0.5～2Torr;
Electrode distance is 21mm;
The silane concentration scope is increased to 4%, 4.5%, 4.75%, 5%, 5.5%, 15% successively since 3%;
Pending sample surfaces temperature: 100-200 ℃;
Doping ratio, promptly foreign atom compares with silicon atom: 0.5～5%.
3. silicon-based thin film solar cell, it is characterized in that: described silicon-based thin film solar cell is unijunction or ties stacked solar cell, cascade solar cell more that described single junction cell structure is a substrate G/ nesa coating T/ boron dopen Nano silicon Window layer P11/ intrinsic silicon base film I1/ phosphorus doping Nano thin film N1/ metal M; Described many knot stacked solar cell, cascade solar cell structures are substrate G/ nesa coating T/ boron dopen Nano silicon Window layer P1/ intrinsic silicon base film I1/ phosphorus doping Nano thin film N1/ boron doped microcrystalline silicon P2/ intrinsic micro crystal silicon thin film I2/ phosphorus doping N type non-crystalline silicon/metal M, and wherein the used N1 layer film of silicon-based thin film solar cell is the described wide bandgap N type nano silicon material of claim 1.
4. silicon-based thin film solar cell according to claim 3 is characterized in that: metal M can be Al or Ag.
5. silicon-based thin film solar cell according to claim 3 is characterized in that: the Voc of amorphous silicon battery is greater than 0.9V, microcrystal silicon battery V
OcGreater than 0.5eV.
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| CN102082188A (en) * | 2010-10-27 | 2011-06-01 | 新奥光伏能源有限公司 | Solar cell window layer material and preparation method and application thereof |
| TW201324818A (en) * | 2011-10-21 | 2013-06-16 | Applied Materials Inc | Method and apparatus for fabricating silicon heterojunction solar cells |
| CN102956756A (en) * | 2012-11-21 | 2013-03-06 | 浙江正泰太阳能科技有限公司 | Manufacturing method and structure of solar battery |
| CN103531713B (en) * | 2013-07-05 | 2016-06-08 | 深圳清华大学研究院 | The preparation method of inorganic nano-crystal/conjugated polymers hybrid solar cell |
| CN103602957A (en) * | 2013-11-07 | 2014-02-26 | 中山市创科科研技术服务有限公司 | Equipment for preparing alpha_SiH membrane |
| CN105552143B (en) * | 2016-02-06 | 2017-08-01 | 中国华能集团清洁能源技术研究院有限公司 | N-type doping silicon thin film, its preparation method and the solar cell including it |
| CN113093010A (en) * | 2021-04-28 | 2021-07-09 | 合达信科技集团有限公司 | Lithium ion battery consistency evaluation method |
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