CN103022245A - Oxygen containing precursors for photovoltaic passivation - Google Patents

Oxygen containing precursors for photovoltaic passivation Download PDF

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CN103022245A
CN103022245A CN2012104786419A CN201210478641A CN103022245A CN 103022245 A CN103022245 A CN 103022245A CN 2012104786419 A CN2012104786419 A CN 2012104786419A CN 201210478641 A CN201210478641 A CN 201210478641A CN 103022245 A CN103022245 A CN 103022245A
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silane
silicon
layer
saturated
deposition
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CN103022245B (en
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M·K·哈斯
A·玛利卡朱南
R·G·里德格瓦伊
K·A·胡特奇松
M·T·萨沃
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Air Products and Chemicals Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/547—Monocrystalline 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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 discloses a passivation layer depositing method on a photovoltaic cell. The method comprises passivation and at least two passivation layers which further comprises a monox layer and a silicon nitride layer. A silicon precursor used for depositing the monox layer or the silicon nitride layer is selected from Si(OR1)Xr2y family or SiRxHy family, and silicane and combination thereof. x+y=4. Y is not equal to 4. R1 is C1-C8 alkyl group. R2 is selected from hydrogen, C1-C8 alkyl group, and NR*3. R is C1-C8 alkyl group or NR*3. The R* can be hydrogen or C1-C8 alkyl group. The C1-C8 alkyl group can be a linear chain, a branch, or annular. A ligand is saturated, unsaturated, or aromatic (for Cyclic alkyl). A photovoltaic device comprising the passivation layer is also disclosed.

Description

What be used for the photovoltaic passivation contains the oxygen precursor
The cross reference of related application
The application requires the U.S. Provisional Application No.61/536 of proposition on September 20th, 2011,748 rights and interests, and its whole disclosures are introduced reference herein.
Technical field
The present invention relates to the field by the silicon-based dielectric material of CVD method manufacturing.Particularly, it relates to for the preparation of the method for the film of this class material and they are as the passivation in the photovoltaic device or the purposes of barrier coat.
Background technology
Photovoltaic (PV) battery becomes electric energy with transform light energy.Many photovoltaic cells utilize monocrystalline silicon or polysilicon as the substrate manufacturing.Silicon substrate in the battery adopts the dopant modification of plus or minus conduction type usually, and its thickness is about the 50-500 micron.In this application, the intention of described substrate (for example wafer) is appointed as front surface towards the surface of incident light, and the surface opposite with front surface is called the rear surface.By convention, the silicon that is just mixing is often referred to and is decided to be " p ", and wherein the hole is majority carrier.The negative silicon that mixes is appointed as " n ", and wherein electronics is majority carrier.The key of photovoltaic cell work is to form the P-N knot, usually forms (Fig. 1) by further coating thin layer at the front surface place of silicon substrate.Layer like this is commonly referred to emitter layer, and bulk silicon is called absorbed layer.Depend on the configuration of device, emitter can be that p mixes or the n doping.
The key request of optimum photovoltaic device efficiency is the front surface of silicon and effective passivation of rear surface.Therefore the surperficial typical earth surface of any solid reveals and the periodic major rupture of body crystal, and produces the higher substoichiometric bonding colony that causes electric defective.For silicon, when these defectives betided in the bandgap range aspect energy, their increased the compound and negative effect device efficiency of charge carrier.When silicon face covered passivation layer (PL), it is crucial that the performance of silicon-PL becomes.And then, because the existence of non-silicon atom causes the crystal of bulk silicon periodically to interrupt at the interface.
Silicon-PL interface charge can play a key effect in affecting passivation effectiveness.Can in lower floor's silicon, form induction field (Aberle, Progress in Photovoltaics, 8,473) at the fixed charge that produces between the PL depositional stage.For the passivation layer that contacts with N-shaped silicon, expectation be that higher positive fixed charge is compound to reduce charge carrier.For the passivation layer that contacts with p-type silicon, expectation to be the positive fixed charge that reduces compound and prevent parasitic shunting to reduce charge carrier.
Except the function that plays passivation layer, dielectric material can provide antireflective property to reduce reflectivity and to increase light absorption.
By Leguit and Wanka method (WO08043827A for the manufacture of the photovoltaic device of having integrated the SiNxHy passivation has been described; Solar Energy Materials and Solar Cells, 40,297), wherein adopt silane and ammonia deposit passivation layer.This method causes at the interface usually greater than+1e12/cm 2High positive fixed charge.Therefore this method is suitable for the passivation that contact with N-shaped silicon, but when contacting with p-type silicon generation poor outcome (Dauwe, Progress in Photovoltaics, 10,271).
US2009151784A has described the method for the manufacture of the photovoltaic device of having integrated hot growing silicon oxide.This method needs the high temperature of 800-1000 ℃ of scope and can cause the slowly processing time.Known this method produces the e11/cm compatible with the passivation of p-type silicon face 2About Fixed interface charge.
Naber has also described the method (34 for the manufacture of the photovoltaic device of having integrated the chemically grown silica ThIEEE PVSC 2009).This method need to have the nitric acid treatment of the long dip time of possibility.
Hofmann has described use silane and N 2O, O 2Or the method (Advances in Optoelectronics, 485467) of photovoltaic device of the lamination of CVD oxide/nitrogenize has been integrated in the ammonia manufacturing.This method has been reported the surface recombination velocity that is lower than 700cm/s for the double-layer overlapped layer system.Next, annealing was brought down below 50cm/s with the carrier lifetime measured value in 15 minutes in 425 ℃ formation gas (forming gas).About 850 ℃ of lower heat treatments approximately increased carrier lifetime in 3 seconds to＜70cm/s.Because be present in the Si-H bond strength in the silane precursor, the deposition of silane oxide film may need high plasma power density and depositing temperature.
Krygowski has described the method (PVSC, 2007) that is used to form passivating coating and forms simultaneously the P-N knot.Precursor such as tetraethyl orthosilicate (TEOS) are used for coated substrate under liquid phase.Surpassing under 700 ℃ the temperature hot activation chemical substance in air (containing oxygen) environment.
Leguijt has described the method (WO08043827A that utilizes tetraethyl orthosilicate (TEOS) to form the silica passivation film; Solar Energy Materials and Solar Cells, 40,297).Utilize TEOS and as the N of oxygen source 2O deposition PECVD film, two kinds of chemical substances are 1: 1 ratio.All samples directly show afterwards in deposition＞and 10 5The surface recombination velocity of cm/sec (SRV).Annealing is after 30 minutes in 400 ℃ formation gas, and the surface recombination velocity that directly measures is between 600-5000cm/sec.These samples show the degeneration with the annealing in process time.
Hoex has described the method (JVST A, 2006) of utilizing TEOS, HMDO (HMDSO) or octamethylcy-clotetrasiloxane (OMCTS) to form the silica passivation film as the PECVD silicon precursor.The film of research utilizes the excess of oxygen deposition.Post-depositional SRV value＞10 3Cm/sec.The deposition after annealing is after 15 minutes in 600 ℃ formation gas, and the SRV value on the N-shaped FZ silicon is 54cm/sec.
Therefore, still need to utilize the precursor that the excellent interface performance that contacts with p-type silicon is provided, do not need extra long-time after annealing step being lower than 450 ℃ depositing temperature deposit, with can industrial output with have into original deposition CVD oxide passivation film or layer.Randomly, can be at the top of sull depositing nitride film (Fig. 2).Passivation layer can be present in front side, rear side or this both sides of device.
Summary of the invention
The present invention relates to the method for the preparation of the passivation layer of photovoltaic device; And photovoltaic device.
In one aspect, provide the method that in chamber, deposits at least one passivation layer at photovoltaic cell, comprised step:
Photovoltaic cell with front surface and rear surface is provided;
The first silicon precursor is provided;
At least one surface at photovoltaic cell deposits the silicon oxide layer with 5-70nm ranges of thicknesses;
The second silicon precursor is provided;
Nitrogenous source is provided; And
Deposit the silicon nitride layer with 20-200nm ranges of thicknesses at silicon oxide layer;
This at least one passivation layer that wherein has the 25-600nm ranges of thicknesses comprises that at least one comprises the bilayer of described silicon oxide layer and described silicon nitride layer.
In yet another aspect, provide a kind of photovoltaic device, having comprised:
Photovoltaic cell, it comprises:
Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
Front surface and rear surface;
And at least one passivation layer that deposits at least one surface of photovoltaic cell by disclosed method.
Again aspect another, a kind of photovoltaic device is provided, comprising:
Photovoltaic cell, it comprises:
Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
Front surface and rear surface;
And at least one passivation layer that is deposited at least one the lip-deep 25-600nm of having ranges of thicknesses of photovoltaic cell;
Wherein this passivation layer has the bilayer of the silicon nitride layer of at least one silicon oxide layer that comprises the 5-70nm ranges of thicknesses and 20-200nm ranges of thicknesses.
Silicon oxide layer in the passivation layer is selected from Si (OR by utilization 1) xR 2 yAt least a silicon precursor deposition of family, wherein
X+y=4, and y ≠ 4;
R 1Be independently selected from
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And R 2Be independently selected from
Hydrogen;
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein part can be saturated, undersaturated or aromatic; With
NR 3 3, R wherein 3Can be independently selected from the saturated or unsaturated alkyl of hydrogen and straight chain, side chain, ring-type.
Silicon nitride layer in the passivation layer is selected from silane, SiR by utilization xH yAt least a silicon precursor deposition of family and their combination;
X+y=4 wherein, y ≠ 4; And
R is independently selected from the C1-C8 straight chained alkyl, and wherein this part is saturated or undersaturated; The example is methyl, ethyl, butyl, propyl group, hexyl, vinyl, pi-allyl, 1-cyclobutenyl, 2-cyclobutenyl;
C 1-C8 branched alkyl, wherein this part can be saturated or unsaturated; The example is isopropyl, isopropenyl, isobutyl group, the tert-butyl group;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; The example is cyclopenta, cyclohexyl, benzyl, methylcyclopentyl; And
NR * 3, R wherein *Can be hydrogen independently; Or the saturated or unsaturated alkyl of straight chain, side chain, ring-type.
Oxide skin(coating) randomly utilizes interpolation oxygen source, for example O 2, N 2O, ozone, hydrogen peroxide, NO, NO 2, N 2O 4Or its mixture to chamber deposits.
Nitrogenous source includes, but are not limited to NH 3, methylamine, dimethylamine, trimethylamine or its mixture.
From Si (OR 1) xR 2 yThe example of the silicon precursor of family includes, but are not limited to methoxy silane, dimethoxy silane, trimethoxy silane, tetramethoxy-silicane, tetrapropoxysilane, Ethoxysilane, diethoxy silane, triethoxysilane, the dimethoxy diethoxy silane, the methoxyl group triethoxysilane, the ethyoxyl trimethoxy silane, methyl ethoxy silane, the ethyl Ethoxysilane, the ethyl diethoxy silane, ethyl triethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, the diethyl diethoxy silane, methyl ethoxy silane, the ethyl Ethoxysilane, methyltrimethoxy silane, trimethylethoxysilane, the n-pro-pyl triethoxysilane, the isopropyl triethoxysilane, ne-butyltriethoxysilaneand, tert-butyl group triethoxysilane and isobutyl triethoxy silane.
From SiR xH yThe example of the silicon precursor of family includes, but are not limited to methyl-monosilane, dimethylsilane, trimethyl silane, tetramethylsilane, ethylsilane, diethylsilane, tetraethyl silane, propyl silane, dipropyl silane, isobutyl group silane, t-butylsilane, dibutyl silane, Methylethyl silane, the dimethyl diethylsilane, the methyl triethyl silicane, ethyl trimethyl silane, isopropyl silane, diisopropyl silane, tri isopropyl silane, diisopropylaminoethyl silane, amino silane, diamino silanes, methylamino silane, ethylamino silane, the diethyl amino base silane, the dimethylamino base silane, di-t-butyl amino silane and diisopropylaminoethyl (ethylene methacrylic base silane).
Brief Description Of Drawings
There is the representative photovoltaic device configuration of four kinds of passivation layer in Fig. 1;
Fig. 2 is coated with the silica passivation layer schematic diagram of optional silicon nitride layer;
Fig. 3 has the curve chart that the minority carrier lifetime of the p-type silicon of passivation layer (bilayer that comprises tetraethyl orthosilicate (TEOS) oxide skin(coating) and the triethyl silicane nitride second layer) changes with minority carrier density.
Embodiment
In one aspect, the present invention relates to for the preparation of the passivation layer of photovoltaic device or the deposition process of film.
One of described method comprises step:
Photovoltaic cell with front surface and rear surface is provided;
Silicon precursor is provided;
Silicon oxide layer deposited at least one surface of photovoltaic cell, wherein passivation layer is this silicon oxide layer.
Silicon precursor is selected from Si (OR 1) xR 2 yFamily; Wherein
X+y=4, and y ≠ 4;
R 1Be independently selected from
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic.
And
R 2Be independently selected from
Hydrogen;
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic;
NR 3 3, R wherein 3Can be independently selected from the saturated or unsaturated alkyl of hydrogen and straight chain, side chain, ring-type.
Silicon oxide layer can be selected from O by interpolation 2, N 2O, ozone, hydrogen peroxide, NO, NO 2, N 2O 4And composition thereof oxygen source deposit.
If use oxygen source and oxygen source volume flow less than 20% of silicon precursor volume flow, then this use that is lower than the oxygen source level of stoichiometric or catalysis can be played the effect of accelerating deposition rate, and still depends on the silicon precursor part simultaneously to form the body of silicon oxide film.
Sull is not more preferably adding the situation deposit of oxygen source in the CVD reative cell.
Do not expect to be bound by theory, have lower or can improved film and chamber uniformity (chamber uniformity) without the situation deposit of the Oxygen source stream of adding.
Layer in addition optionally is deposited on the top of silicon oxide layer.For example, silicon nitride, carborundum, carbonitride of silicium, transparent conductive oxide, aluminium oxide, amorphous silicon.
For example, but cvd nitride silicon thin film (or layer) with the silicon oxide film on one or two silicon face that covers photovoltaic device (or layer).
Another kind method comprises step:
Photovoltaic cell with front surface and rear surface is provided;
The first silicon precursor is provided;
Silicon oxide layer deposited at least one surface of photovoltaic cell;
The second silicon precursor is provided;
Nitrogenous source is provided; And
Deposited silicon nitride layer on silicon oxide layer;
Wherein passivation layer comprises bilayer, and this bilayer comprises this silicon oxide layer and this silicon nitride layer.
The first silicon precursor is selected from Si (OR 1) xR 2 yFamily; Wherein
X+y=4, and y ≠ 4;
R 1Be independently selected from
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic.
And R 2Be independently selected from
Hydrogen;
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And
NR 3 3, R wherein 3Can be independently selected from the saturated or unsaturated alkyl of hydrogen and straight chain, side chain, ring-type.
The second silicon precursor is selected from silane, SiR xH yFamily; X+y=4 wherein, y ≠ 4, and R is independently selected from the C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated; The example is methyl, ethyl, butyl, propyl group, hexyl, vinyl, pi-allyl, 1-cyclobutenyl, 2-cyclobutenyl; The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated; The example is isopropyl, isopropenyl, isobutyl group, the tert-butyl group; The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; The example is cyclopenta, cyclohexyl, benzyl, methylcyclopentyl; And NR * 3, R wherein *Can be the saturated or undersaturated alkyl of hydrogen or straight chain, side chain, ring-type independently.
In this case, passivation layer is the bilayer with silicon oxide layer and silicon nitride layer.
Silicon oxide layer can be selected from O by interpolation again 2, N 2O, ozone, hydrogen peroxide, NO, NO 2, N 2O 4And composition thereof oxygen source deposition.
For example, passivation layer can be double-deck, and wherein silicon nitride layer is by adopting silane and ammonia deposition.
Passivation layer can also comprise a plurality of bilayers.
The invention still further relates to photovoltaic device, comprising:
Photovoltaic cell, it comprises:
Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
Front surface and rear surface;
And utilization is selected from Si (OR 1) xR 2 yAt least a silicon precursor of family is deposited at least one lip-deep at least one passivation layer of photovoltaic cell, wherein
X+y=4, and y ≠ 4;
R 1Be independently selected from
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic.
And R 2Be independently selected from
Hydrogen;
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And
NR 3 3, R wherein 3Can be independently selected from the saturated or unsaturated alkyl of hydrogen and straight chain, side chain, ring-type;
Wherein passivation layer is silicon oxide film.
The invention still further relates to a kind of photovoltaic device, comprising:
Photovoltaic cell, it comprises:
Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
Front surface and rear surface;
And be deposited at least one lip-deep at least one passivation layer; Wherein this at least one passivation layer utilization is selected from Si (OR 1) xR 2 yThe first silicon precursor deposition of family; Wherein
X+y=4, and y ≠ 4;
R 1Be independently selected from
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic;
And R 2Be independently selected from
Hydrogen;
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And
NR 3 3, R wherein 3Can be independently selected from the saturated or unsaturated alkyl of hydrogen and straight chain, side chain, ring-type;
And
The second silicon precursor is selected from silane, SiR xH yFamily and their combination; Wherein
X+y=4, y ≠ 4; And
R is independently selected from
The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And
NR * 3, R wherein *Can be independently selected from the saturated or undersaturated alkyl of hydrogen and straight chain, side chain, ring-type.
Preferably, the C1-C8 straight chained alkyl is selected from the group that is comprised of methyl, ethyl, butyl, propyl group, hexyl, vinyl, pi-allyl, 1-cyclobutenyl and 2-cyclobutenyl; The C1-C8 branched alkyl is selected from the group that is comprised of isopropyl, isopropenyl, isobutyl group and the tert-butyl group; The C1-C8 cycloalkyl is selected from the group that is comprised of cyclopenta, cyclohexyl, benzyl and methylcyclopentyl.
In this case, passivation layer is the bilayer with silicon oxide layer and silicon nitride layer.
Silicon oxide layer or film can utilize and be selected from O 2, N 2O, ozone, hydrogen peroxide, NO, NO 2, N 2O 4And composition thereof the oxygen source deposition of interpolation.
Sull more preferably deposits in the situation that does not have the oxygen source that adds to the CVD reative cell.
The deposition of silicon nitride layer/film can be utilized and include, but are not limited to NH 3, methylamine, dimethylamine, trimethylamine or its mixture nitrogenous source.
The silicon precursor that is suitable for silicon oxide layer deposited among the present invention includes, but are not limited to: methoxy silane, dimethoxy silane, trimethoxy silane, tetramethoxy-silicane, four positive propoxy silane (or tetrapropoxysilane), Ethoxysilane, diethoxy silane, triethoxysilane, tetraethyl orthosilicate ester (or tetraethoxysilane), the dimethoxy diethoxy silane, the methoxyl group triethoxysilane, the ethyoxyl trimethoxy silane, methyl ethoxy silane, the ethyl Ethoxysilane, the ethyl diethoxy silane, ethyl triethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, the diethyl diethoxy silane, methyldiethoxysilane, methyl ethoxy silane, the ethyl Ethoxysilane, methyltrimethoxy silane, trimethylethoxysilane, the n-pro-pyl triethoxysilane, the isopropyl triethoxysilane, ne-butyltriethoxysilaneand, tert-butyl group triethoxysilane, isobutyl triethoxy silane.
The silicon precursor that is suitable for deposited silicon nitride layer among the present invention includes, but are not limited to: methyl-monosilane, dimethylsilane, trimethyl silane, tetramethylsilane, ethylsilane, diethylsilane, triethyl silicane, tetraethyl silane, propyl silane, dipropyl silane, isobutyl group silane, t-butylsilane, dibutyl silane, Methylethyl silane, the dimethyl diethylsilane, the methyl triethyl silicane, ethyl trimethyl silane, isopropyl silane, diisopropyl silane, tri isopropyl silane, diisopropylaminoethyl silane, amino silane, diamino silanes, methylamino silane, ethylamino silane, the diethyl amino base silane, the dimethylamino base silane, di-t-butyl amino silane and diisopropylaminoethyl (ethylene methacrylic base silane).
Should be understood that silicon oxide layer/film also refers to be silicon dioxide layer/film.Silicon oxide layer can comprise carbon and the hydrogen of low concentration.Carbon atom concn preferably is lower than 5% atom, and hydrogen atom concentration is lower than 20% atom.
Should be understood that silicon nitride layer/film can comprise measurable hydrogen concentration, consistent with amorphous thin film known in the art.
In one embodiment, photovoltaic cell for example according to photovoltaic cell of the present invention, adopts the doped substrate the comprise silicon form of wafer or band (typically with) to make.Described substrate can comprise monocrystalline silicon or polysilicon.Unless explicitly point out, " silicon " as used herein comprises monocrystalline silicon and polysilicon.If necessary, the layer of one or more additional materials (for example germanium) can be placed on the substrate surface or be incorporated in the described substrate.Although boron is widely used as the p-type dopant, also can adopt other p-type dopants for example gallium or indium.Although phosphorus is widely used as the N-shaped dopant, can adopt other dopants.Therefore, photovoltaic cell, silicon substrate or substrate are interchangeable.
Typically obtain silicon substrate by cutting silicon ingot, vapour deposition, rheotaxial growth or other known methods.Cutting can rely on inner diameter blade, continuous metal line or other known cutting methods to be carried out.Although substrate can be cut into the shape of any general plane, yet wafer typically is circle.Usually, this wafer is usually less than about 500 micron thick.Preferably, substrate of the present invention is less than about 200 micron thick.
In further first being processed, preferred clean substrate is to remove any surface debris and cutting damage.Typically, this comprises and places wet-chemical to bathe substrate, for example, comprises any one the solution in alkali and peroxide mixture, acid and peroxide mixture, NaOH solution or known in the art and several other solution of using.Clean required temperature and time and depend on the particular solution that adopts.
Randomly (especially for single crystalline substrate), substrate is by for example anisotropic etching texturing of crystal face.Texturing is generally from the form of the Pyramid of substrate surface depression or projection.Height and the degree of depth of Pyramid change with technique, but typically are about 1 to about 7 microns.One or two side of solar cell can be by texturing.
Typically by adopt with body in the dopant that exists have opposite electrical dopant doped substrate formation emitter layer.Can be by at substrate deposition n dopant and heat subsequently described substrate and enter and realize in the substrate that N mixes to order about the n dopant.The gas diffusion can be used for depositing the n dopant to substrate surface.Yet also can use additive method, for example be used in Implantation, solid-state diffusion or this area forming the layer of n doping and the additive method of shallow p-n junction near the substrate surface place.Phosphorus is preferred n dopant, but can use separately or be combined with the n dopant of any appropriate, for example arsenic, antimony or lithium.On the contrary, can adopt similar method to be applied to boron mixes.After emitter forms, along all exposures place formation p-n junctions of substrate surface.In some embodiments, during ensuing processing, may be necessary to remove the zone of mixing from side or the edge of wafer.
The emitter doping treatment can produce one deck silica at the exposed surface of wafer, and it was removed before applying passivating coating usually.By for example chemical etching in wet-chemical is bathed, typically in low concentration HF solution, remove this silica.
In one embodiment, in order to form the selective emitter zone, can carry out subsequently local high density and mix.
Before deposit passivation layer or film, can utilize acidity as known in the art or alkaline solution to clean substrate.
Film of the present invention deposition is compatible with various chemical technologies for the manufacture of photovoltaic device, and can be attached on the multiple material.For example, this deposition is chemical vapour deposition (CVD) (CVD) or plasma enhanced chemical vapor deposition (PECVD).
In the execution mode of bilayer, it is thick that silicon oxide layer typically is 5-70nm, preferred 5-45nm; And silicon nitride layer typically is 20-200nm, and preferred 30-150nm is thick.Passivation layer can have a plurality of bilayers.Passivation layer of the present invention is sink to usually approximately 25-600nm, preferably 40 to about 500nm gross thickness.Thickness can be changed as required, a bilayer (comprising silicon oxide layer and silicon nitride layer) and/or a plurality of bilayer can be adopted.
Preferably, passivation film according to the present invention has between 1.0-4.0, more preferably the refraction coefficient between the 1.7-2.3.Can utilize 2 or a plurality of film to realize improved reflectivity on the wave-length coverage.For example, utilize the more layers according to antireflecting coating of the present invention, reflectivity is can minimized wave-length coverage larger.Typically for a plurality of layers, each layer has different refraction coefficients.
Liquid precursor can be transported to reaction system by many kinds of modes, preferably adopts suitable valve and accessory to be housed to allow carrying liquid to the pressurization rustless steel container for the treatment of reactor.
Before the deposition reaction, during and/or afterwards, can add other material in the vacuum chamber.This material for example comprises, inert gas is (such as He, Ar, N 2, Kr, Xe etc., it can be used as the carrier gas of the less precursor of volatility) and reactive materials, for example gas or fluid organic material matter, NH 3And H 2
Apply energy to gaseous reagent, thereby induce gas to react and form layer/film at substrate.Can provide this energy by for example heat, plasma, pulsed plasma, Helicon wave plasma, high-density plasma, inductively coupled plasma and remote plasma process (depending on the method that adopts).The 2nd rf radio frequency source can be used for changing the plasma characteristics at substrate surface place.Preferably, utilize plasma enhanced chemical vapor deposition to form coating.The plasma frequency scope depends on depositing system, for 10KHz arrives 40MHz.Chamber configuration can be for single or multiple wafers, and direct or remote plasma.
The flow velocity of each gaseous reagent preferably is in the scope of 10-10000sccm, and highly depends on the volume of chamber.The flow velocity of silicon precursor preferably is in the scope of 10sccm-1700sccm; The flow velocity of oxygen source preferably is in the scope of 2-17000sccm; And the flow velocity of nitrogenous source preferably is in the scope of 200-17000sccm.
The method of adding the contact of photovoltaic battery wafers substrate is well known in the art.Adopt one of multiple known method with front with after contact and be applied to substrate: photoetching, laser grooving and electroless plating, silk screen printing or other any methods, it provides respectively and contacts with the good ohmic of rear surface with front, thereby draws electric current from photovoltaic cell.Typically, contact exists by design or pattern, such as grid, finger-like, wire etc., and do not cover whole front or rear surface.After applying contact, can toast substrate (short annealing or heat treatment), several seconds only under the about 950 ℃ temperature of about 700-typically, 1-10 second for example, thus form contact on the substrate.
Fig. 1 shows four kinds of possible device configurations.The present invention and p-n junction wherein are formed on the device compatible (Fig. 1 a, 1b, 1c) of device front side.
The present invention also, fourchette tactile around connecting with for example metal back of the body contact device configuration that contacts before (Fig. 1 d) or the fourchette compatible.In these devices, p-n junction is not formed uniformly in the device front side.Yet effectively passivation layer/film still is crucial for device performance.
Owing to utilizing the refraction coefficient of passivation layer/film that the present invention forms for the impact of Fresnel reflection degree in the full angle scope, when this passivation layer/film is used on the device rear side, can provide the benefit that increases internal reflection.The internal reflection rate that increases provides higher device efficiency usually.
When the passivation layer/film that utilizes the present invention to produce was used for the device front side, it can provide antireflecting additional benefit.Layer/film thickness can minimize the amount of the light that reflects away from the device front side with respect to the optimization of refraction coefficient.The front-reflection that reduces causes the device efficiency that improves usually.
Passivation layer/the film that utilizes the present invention to produce can significantly not degenerated in 4 seconds process of 800 ℃ of lower bakings.Preferably, 20% minimizing surface lifetime appears being lower than.More preferably, surperficial carrier lifetime improves.
Passivation layer with a double-deck lamination has the surface recombination life value less than 200cm/sec, and is preferred＜100cm/sec, and most preferably＜30cm/sec.
Can describe in more detail the present invention with reference to following embodiment, it should be understood that the present invention is not limited to this.
Embodiment
The Dmol3 module based on Density functional of the Materials Studio bag that utilization can commercial be obtained is carried out bond energy and is calculated.
Clean to remove organic and metal surface impurity and HF surface treatment with after removing all living oxides (native oxide) at three step RCA, the p-type Float Zone silicon substrate with 1000-2000 Ω-cm resistivity is carried out the deposition of embodiment 2-4.
For embodiment 5-7, deposit at the p-type Float Zone silicon substrate with 1-5 Ω-cm resistivity.
These silicon substrates are all 500 microns.
In order to utilize the Sinton life-span tester to measure surperficial recombination lifetime, deposit in the both sides of silicon substrate.
Under 13.56MHz, on 200mm single-chip PECVD platform, deposit.The depositing temperature scope is 200-450 ℃.The chamber pressure scope is the 2-10 holder.The electrode spacing scope is 200-800mil.
To whole embodiment, the silicon oxide layer of Direct precipitation 15nm on silicon substrate, and cover the silicon nitride layer of 85nm at silicon oxide layer.
Embodiment 1
Table 1 shows the bond energy for silane and the calculating of several alkoxy silane.Compared to silane, the form that alkoxyl replaces has the lower part of thermodynamics bond energy.Do not expect to be bound by theory, suppose that lower bond energy (being O-C) allows to form silica under than low plasma power density and depositing temperature, thereby the inactivating performance of enhancing is provided.Suppose the high bond strength of Si-O in the compound so that this material is retained in the plasma and permission deposits in the situation of not adding independent oxygen source.
The bond energy of Table I silane and alkoxy silane molecular computing.
Molecule The Si-H bond energy The O-C bond energy The Si-O bond energy
Silane 95kcal/mol N/A N/A
Trimethoxy silane 97kcal/mol 86kcal/mol 100kcal/mol
Tetramethoxy-silicane N/A 87kcal/mol 112kcal/mol
Four positive propoxy silane N/A 84kcal/mol 111kcal/mol
The tetraethyl orthosilicate ester N/A 86kcal/mol 108kcal/mol
Embodiment 2
Thereby utilize tetraethyl orthosilicate or tetraethoxysilane or TEOS to deposit at the surface of silicon substrate deposition 15nm silicon oxide layer/film.The independent oxygen source that does not add is used for deposition process.
For the silicon nitride layer of 85nm, triethyl silicane and ammonia are used at the top of silicon oxide film this layer of deposition.
The flow velocity that is used for the silica deposition is: be 500mg/min or 53.8sccm for TEOS; Be 1000sccm for He.Chamber pressure is 8 holders; Power is 910W.Depositing temperature is set to 400 ℃.
The flow velocity that is used for the silicon nitride deposition is 125mg/min or 24sccm for triethyl silicane; For NH 3Be 225sccm; Be 400sccm for He.Chamber pressure is 3 holders; Power is 400W.Depositing temperature is set to 350 ℃.
Deposit TEOS film A and TEOS film B at two substrates under the same deposition condition.
Utilize the Sinton life test to collect lifetime data and record like the minority carrier lifetime value for 1e15 and 5e14 with transient mode.Table II shows life-span and recombination-rate surface.
Table II is without O 2Minority carrier lifetime and the recombination-rate surface of TEOS film after the PECVD deposition
Figure BSA00000810011700151
Utilize equation SRV=t/2 (T) to determine recombination-rate surface, wherein t is that unit is that the silicon thickness of cm and T are the measurement life-spans that unit is second.Each film causes the SRV value less than 160cm/sec, (the Advances in Optoelectronics such as this and Hofman, 485467) opposite, after its report does not use and utilizes monosilane cvd silicon oxide and silicon nitride in the situation of heat treatment (for example toast and/or anneal), for the SRV value of the 700cm/sec of bilayer.
Embodiment 3
Under 800 ℃ of peak temperatures, utilize band oven heating from the TEOS film of embodiment 2 less than 10 seconds.
Table III shows life-span and recombination-rate surface.
Table III. minority carrier lifetime and the recombination-rate surface of TEOS film after short annealing (R.A.) heat treatment
Figure BSA00000810011700152
In about 800 ℃ of lower heat treatments only after the several seconds, the surface recombination life value improves and surpasses 150%.
Typical heat treatment causes the obvious improvement in life-span during the screen-printed metal.Compared to prior art, the improvement of inactivating performance appears at during the existing metallization process, thereby needn't add annealing steps in whole process sequence.
Embodiment 4
Except the oxygen source that adds, utilize with embodiment 2 in identical condition deposit.Utilize oxygen source O that add, independent 2, TEOS is used for the silicon oxide layer/film at the surface of silicon substrate deposition 15nm.
For the silicon nitride layer of 85nm, triethyl silicane and ammonia are used at the top of silicon oxide film this layer of deposition.
The flow velocity that is used for the silica deposition: be 500mg/min or 53.8sccm for TEOS; For O 2Be 1000sccm; And be 1000sccm for He.Chamber pressure is 8 holders; Power is 910W.Depositing temperature is set to 400 ℃.
The flow velocity that is used for the silicon nitride deposition is 125mg/min or 24sccm for triethyl silicane; For NH 3Be 225sccm; Be 400sccm for He.Chamber pressure is 3 holders; Power is 400W.Depositing temperature is set to 350 ℃.
Deposit TEOS film C and TEOS film D at two substrates under the same deposition condition.
Table IV shows life-span and recombination-rate surface.
Table IV. use O 2PECVD deposition after minority carrier lifetime and the recombination-rate surface of TEOS film
In the situation that do not toast or short annealing, the surface recombination life value is＜30cm/sec.
Embodiment 5
Be used for oxide deposition and triethyl silicane with front embodiment 4 identical ground TEOS and be formed at the FloatZone silicon with 1-5 Ω-cm resistivity for the passivation stack that the 15nm silica by being coated with the 85nm silicon nitride of nitride deposition consists of.
For the silicon oxide layer of 15nm, utilize tetraethyl orthosilicate (TEOS) to deposit, thereby on the surface of silicon substrate the deposition oxide film.In depositing operation, independent oxygen source uses with TEOS.
For the silicon nitride layer of 85nm, triethyl silicane and ammonia are used at silicon oxide film top this layer of deposition.
The flow velocity that is used for the silica deposition: be 500mg/min or 53.8sccm for TEOS; For O 2Be 1000sccm; And be 1000sccm for He.Chamber pressure is 8 holders; Power is 800W.Depositing temperature is set to 350 ℃.
The flow velocity that is used for the silicon nitride deposition is 125mg/min or 24sccm for triethyl silicane; For NH 3Be 225sccm.Chamber pressure is 3 holders; Power is 400W.Depositing temperature is set to 350 ℃.
The passivation layer of deposition produces the silicon device of the SRV of minority carrier lifetime with 373 μ sec and/or 134cm/sec.
Because there is not measurable difference in carrier lifetime under 5e14 or 1e15, thereby minority carrier lifetime and SRV average at 5e14 or 1e15 place.
Embodiment 6
Under the condition that is similar to embodiment 5, carry out embodiment 6, carry out the deposition of triethyl silicane nitride with the life-span that obtains to optimize except utilizing the BKM parameter.
For the silicon oxide layer of 15nm, utilize tetraethyl orthosilicate (TEOS) to deposit, thereby on the surface of silicon substrate the deposition oxide film.In depositing operation, independent oxygen source uses with TEOS.
For the silicon nitride layer of 85nm, triethyl silicane and ammonia are used at silicon oxide film top this layer of deposition.
The flow velocity that is used for the silica deposition: be 500mg/min or 53.8sccm for TEOS; For O 2Be 1000sccm; Be 1000sccm for He.Chamber pressure is 8 holders; Power is 800W.Depositing temperature is set to 350 ℃.
The flow velocity that is used for the silicon nitride deposition is 100mg/min or 19.3sccm for triethyl silicane; For NH 3Be 800sccm.Chamber pressure is 3 holders; Power is 400W.Depositing temperature is set to 400 ℃.
The passivation layer of deposition produces the silicon device of the SRV of minority carrier lifetime with 433 μ sec or 115cm/sec.
Embodiment 7
Under the condition that is similar to embodiment 6, carry out embodiment 7, carry out TEOS oxide deposition and triethyl silicane nitride deposition with the life-span that obtains optimization except utilizing the BKM parameter.
For the silicon oxide layer of 15nm, utilize tetraethyl orthosilicate (TEOS) to deposit, thereby on the surface of silicon substrate the deposition oxide film.In depositing operation, independent oxygen source uses with TEOS.
For the silicon nitride layer of 85nm, triethyl silicane and ammonia are used at silicon oxide film top this layer of deposition.
The flow velocity that is used for the silica deposition: be 165mg/min or 53.8sccm for TEOS; For O 2Be 1365sccm; Be 650sccm for He.Chamber pressure is 8 holders; Power is 200W.Depositing temperature is set to 375 ℃.
The flow velocity that is used for the silicon nitride deposition is 100mg/min or 19.3sccm for triethyl silicane; For NH 3Be 800sccm.Chamber pressure is 3 holders; Power is 400W.Depositing temperature is set to 400 ℃.
The passivation layer of deposition produces the silicon device of the SRV of minority carrier lifetime with 528 μ sec or 97.7cm/sec.
Front embodiment should be considered as illustrative, rather than limits the present invention who is defined by the claims.Such as appearance intelligible, do not breaking away from the given situation of the present invention of claim, but the multiple variation of application of aforementioned feature and combination.This variation should be thought and is included in the scope of following claim.

Claims (15)

  1. One kind in chamber in the method for at least one passivation layer of photovoltaic cell deposition, comprise step:
    Photovoltaic cell with front surface and rear surface is provided;
    The first silicon precursor is provided;
    At least one surface at described photovoltaic cell deposits the silicon oxide layer with 5-70nm ranges of thicknesses;
    The second silicon precursor is provided;
    Nitrogenous source is provided; And
    Deposit the silicon nitride layer with 20-200nm ranges of thicknesses at described silicon oxide layer;
    This at least one passivation layer that wherein has the 25-600nm ranges of thicknesses comprises that at least one comprises the bilayer of described silicon oxide layer and described silicon nitride layer.
  2. 2. the process of claim 1 wherein that described the first silicon precursor is selected from Si (OR 1) xR 2 yFamily; Wherein
    X+y=4 and y ≠ 4;
    R 1Be independently selected from
    The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
    The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
    The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic;
    And
    R 2Be independently selected from
    Hydrogen;
    The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
    The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
    The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And
    NR 3 3, R wherein 3Can be independently selected from the saturated or unsaturated alkyl of hydrogen and straight chain, side chain, ring-type; And
    The second silicon precursor is selected from silane, SiR xH yFamily and combination thereof; Wherein
    X+y=4, y ≠ 4, and
    R is independently selected from
    The C1-C8 straight chained alkyl, wherein this part is saturated or undersaturated;
    The C1-C8 branched alkyl, wherein this part can be saturated or unsaturated;
    The C1-C8 cycloalkyl, wherein this part can be saturated, undersaturated or aromatic; And
    NR * 3, R wherein *Can be independently selected from the saturated or unsaturated alkyl by hydrogen and straight chain, side chain, ring-type;
    Preferably, described C1-C8 straight chained alkyl is selected from by methyl, ethyl, butyl, propyl group, hexyl, vinyl, pi-allyl, 1-cyclobutenyl and 2-cyclobutenyl; Preferably, described C1-C8 branched alkyl is selected from isopropyl, isopropenyl, isobutyl group and the tert-butyl group; Preferably, described C1-C8 cycloalkyl is selected from cyclopenta, cyclohexyl, benzyl and methylcyclopentyl.
  3. 3. claim 1 or 2 described methods, wherein said the first silicon precursor is selected from the group that is comprised of following: methoxy silane, dimethoxy silane, trimethoxy silane, tetramethoxy-silicane, tetrapropoxysilane, Ethoxysilane, diethoxy silane, triethoxysilane, the dimethoxy diethoxy silane, the methoxyl group triethoxysilane, the ethyoxyl trimethoxy silane, methyl ethoxy silane, the ethyl Ethoxysilane, the ethyl diethoxy silane, ethyl triethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, the diethyl diethoxy silane, methyl ethoxy silane, the ethyl Ethoxysilane, methyltrimethoxy silane, trimethylethoxysilane, the n-pro-pyl triethoxysilane, the isopropyl triethoxysilane, ne-butyltriethoxysilaneand, tert-butyl group triethoxysilane, isobutyl triethoxy silane and their combination are preferably selected from by tetraethyl orthosilicate, tetrapropoxysilane, the group that diethoxymethyl silane and composition thereof forms; And
    Described the second silicon precursor is selected from the group that is comprised of following: silane, methyl-monosilane, dimethylsilane, trimethyl silane, tetramethylsilane, ethylsilane, diethylsilane, tetraethyl silane, propyl silane, dipropyl silane, isobutyl group silane, t-butylsilane, dibutyl silane, Methylethyl silane, the dimethyl diethylsilane, the methyl triethyl silicane, ethyl trimethyl silane, isopropyl silane, diisopropyl silane, tri isopropyl silane, diisopropylaminoethyl silane, amino silane, diamino silanes, methylamino silane, ethylamino silane, the diethyl amino base silane, the dimethylamino base silane, di-t-butyl amino silane and diisopropylaminoethyl (ethylene methacrylic base silane) and their combination are preferably selected from by triethyl silicane, trimethyl silane, the group that tetramethylsilane and combination thereof form.
  4. 4. each described method among the claim 1-3, wherein deposition process is chemical vapour deposition (CVD) or plasma enhanced chemical vapor deposition.
  5. 5. each described method among the claim 1-4 is wherein carried out described deposition in the situation that do not add oxygen source.
  6. 6. each described method among the claim 1-4 wherein is selected from O by making 2, N 2O, ozone, hydrogen peroxide, NO, NO 2, N 2O 4And composition thereof the interpolation Oxygen source stream carry out the deposition of described silicon oxide layer to described chamber.
  7. 7. each described method among the claim 1-6, the flow velocity that wherein said nitrogenous source flows into described chamber is 500-10000sccm; The flow velocity that described the first silicon precursor and the second silicon precursor flow into described chamber is 10-1700sccm independently.
  8. 8. each described method among the claim 1-7, the temperature deposit of wherein said silicon oxide layer between 200 ℃ to 400 ℃; And the temperature deposit of described silicon nitride layer between 300 ℃ to 450 ℃.
  9. 9. each described method among the claim 1-8, wherein said passivation layer has＜200cm/s, the surface recombination velocity of preferred＜100cm/s and more preferably＜30cm/s.
  10. 10. each described method among the claim 1-9, wherein said silicon oxide layer has the thickness of 5-45nm scope; And described silicon nitride layer has the thickness of 30-150nm scope.
  11. 11. a photovoltaic device comprises:
    Photovoltaic cell, it comprises:
    Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
    Front surface and rear surface; And
    At least one passivation layer that utilizes method claimed in claim 5 to deposit at described photovoltaic cell.
  12. 12. a photovoltaic device comprises:
    Photovoltaic cell, it comprises:
    Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
    Front surface and rear surface; And
    At least one passivation layer that utilizes method claimed in claim 6 to deposit at described photovoltaic cell.
  13. 13. a photovoltaic device comprises:
    Photovoltaic cell, it comprises:
    Adjoin the silicon layer that the P of the silicon layer that N mixes mixes,
    Front surface and rear surface; And
    At least one at least one lip-deep thickness that is deposited on described photovoltaic cell is the passivation layer of 25-600nm scope;
    Wherein said passivation layer has at least one and comprises that thickness is that silicon oxide layer and the thickness of 5-70nm scope is the bilayer of the silicon nitride layer of 20-200nm scope.
  14. 14. the described photovoltaic device of claim 13, wherein said passivation layer has＜200cm/s, the surface recombination velocity of preferred＜30cm/s.
  15. 15. claim 13 or 14 described photovoltaic devices, wherein said silicon oxide layer has the thickness of 5-45nm scope; And described silicon nitride layer has the thickness of 30-150nm scope.
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