CN102097541B - Method for enhancing efficiency of industrial single-chamber deposited amorphous silicon-based solar cell - Google Patents
Method for enhancing efficiency of industrial single-chamber deposited amorphous silicon-based solar cell Download PDFInfo
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- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002708 enhancing effect Effects 0.000 title 1
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 113
- 239000001257 hydrogen Substances 0.000 claims abstract description 113
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000007789 gas Substances 0.000 claims abstract description 57
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 229910021424 microcrystalline silicon Inorganic materials 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 118
- 229910000077 silane Inorganic materials 0.000 claims description 118
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims description 61
- 230000004936 stimulating effect Effects 0.000 claims description 48
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 32
- 238000010790 dilution Methods 0.000 claims description 29
- 239000012895 dilution Substances 0.000 claims description 29
- 239000013081 microcrystal Substances 0.000 claims description 29
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 239000002019 doping agent Substances 0.000 claims description 20
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 20
- 229910000085 borane Inorganic materials 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000078 germane Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 117
- 239000010409 thin film Substances 0.000 abstract description 9
- 238000000862 absorption spectrum Methods 0.000 abstract description 3
- 230000005641 tunneling Effects 0.000 abstract 2
- 230000008092 positive effect Effects 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 description 32
- 238000000151 deposition Methods 0.000 description 17
- 239000010408 film Substances 0.000 description 10
- 239000012495 reaction gas Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
一种提高产业化单室沉积非晶硅基薄膜电池效率的方法，将产业化单室沉积的非晶硅基薄膜太阳电池与窄带隙的微晶硅基太阳电池组成多结叠层太阳电池，对中间的np隧穿结进行工艺设计，形成重掺的掺杂层和良好的隧穿特性，具体步骤如下：1）通过氢等离子工艺刻蚀产业化单室沉积的非晶硅基薄膜太阳电池的非晶硅n层；2）然后通过等离子工艺沉积微晶硅n层；3）最后通过等离子工艺沉积微晶硅基电池。本发明的优点和积极效果：本方法通过氢等离子体处理电池非晶硅n层表面氧化物，然后沉积微晶N和微晶硅底电池，在不需要额外引入其它气体情况下，可以拓宽电池的吸收光谱，获得高的开路电压，提高电池的转换效率。
A method for improving the efficiency of industrialized single-chamber deposition of amorphous silicon-based thin-film solar cells. The industrialized single-chamber deposition of amorphous silicon-based thin-film solar cells and narrow-bandgap microcrystalline silicon-based solar cells form multi-junction stacked solar cells. Process design for the np tunneling junction in the middle to form a heavily doped doped layer and good tunneling characteristics. The specific steps are as follows: 1) Etch the industrialized single-chamber deposited amorphous silicon-based thin film solar cell by hydrogen plasma process The amorphous silicon n-layer; 2) Then deposit the microcrystalline silicon n-layer by plasma process; 3) Finally, deposit the microcrystalline silicon-based battery by plasma process. Advantages and positive effects of the present invention: This method treats the battery amorphous silicon n-layer surface oxide by hydrogen plasma, and then deposits microcrystalline N and microcrystalline silicon bottom cells, and can widen the battery without additionally introducing other gases. Absorption spectrum, obtain high open circuit voltage, improve the conversion efficiency of the battery.
Description
Technical field
The present invention relates to the solar cell field, especially a kind of method that improves industrialization deposited in single chamber amorphous silicon-based film battery efficiency.
Background technology
Photovoltaic generation is attracting increasing people to put into this research field as the important component part of regenerative resource, and almost each country is all paying close attention to the research in this field.As early as possible the photovoltaic generation cost is reduced under the close situation with the conventional energy resource cost of electricity-generating of ability, could really makes it to be widely used.Therefore low-cost, high efficiency solar cell is the target that people pursue always.The deposited in single chamber technology as a kind of manufacturing technology of low-cost silicon-based thin film solar cell, becomes the focus that people pay close attention to.The silicon-based thin film solar cell of industrialization comparative maturity all is deposited in single chamber amorphous silicon film solar battery or amorphous silicon/amorphous silicon laminated thin film solar cell mostly now, and its stabilized conversion efficiency is basically at 5-7%.For improving productive rate, reducing cost, the electrode structure of the PECVD system of this single chamber is parallel placement, and reacting gas gets into the aura district from an end of electrode, and residual gas is taken away at the other end of electrode.If can the photoelectric conversion efficiency of above-mentioned solar cell further be improved, then will increase the range of application of silicon-based thin film solar cell greatly.
Effective ways that improve existing industrialization single chamber manufacturing amorphous silicon-based film solar cell are spectral response ranges of expanding battery, and the sunlight that can not be absorbed and used in the existing industrialization battery is fully utilized.Method is exactly that solar cell with above-mentioned battery and narrow band gap is attached to and forms many knot stacked solar cell, cascade solar cells together.And the silica-based or silica-based binode stacked solar cell, cascade solar cell of amorphous of p-i-n type unijunction amorphous of the glass substrate that the above-mentioned reacting gas of mentioning of the employing of industrialization is made from the single chamber PECVD system of single-ended introducing, its n layer can only be amorphous silicon.But if will itself and the micro crystal silicon solar battery of narrow band gap be formed many knot stacked solar cell, cascade solar cells, the material of the np tunnel junctions in the middle of then requiring is a crystallite, in order to forming heavily doped doped layer, thus the tunnel junctions of structure characteristic good; Can reduce simultaneously the series resistance of stacked solar cell, cascade solar cell, improve the fill factor, curve factor of battery.This just a problem occurs; The amorphous silicon battery that how will make by the single chamber PECVD of the single-ended introducing of reacting gas of aforementioned industrialization extensive use; Micro crystal silicon solar battery combination with narrow band gap realizes wide spectral absorption, with the efficient of further raising deposited in single chamber silicon-based thin film solar cell.
Summary of the invention
The objective of the invention is to above-mentioned existing problems; A kind of method that improves industrialization deposited in single chamber amorphous silicon-based film battery efficiency is provided, and this method can improve the photoelectric conversion efficiency of the silicon-based thin film solar cell of amorphous silicon (or amorphous silicon germanium) unijunction of having realized at present the deposited in single chamber of industrialization or amorphous silicon/amorphous silicon (or amorphous silicon/amorphous silicon germanium) binode.
Technical scheme of the present invention:
A kind of method that improves industrialization deposited in single chamber amorphous silicon-based film battery efficiency; The amorphous silicon-based film solar cell of industrialization deposited in single chamber and the microcrystalline silicon solar cell of narrow band gap are formed many knot stacked solar cell, cascade solar cells; Np tunnel junctions to the centre is carried out technological design; Form heavily doped doped layer and good tunnelling characteristic, concrete steps are following: the amorphous silicon n layer that 1) passes through the amorphous silicon-based film solar cell of hydrogen plasma process etching industrialization deposited in single chamber; 2) then through plasma process deposition micro crystal silicon n layer; 3) at last through plasma process deposition micro crystal silicon base battery.
The technological parameter of the amorphous silicon n layer of the amorphous silica-based solar cell of said etching industrialization is: reacting gas is a hydrogen, and reacting gas pressure is greater than 0.5Torr; Glow power density (0.1-3) W/cm
2Aura stimulating frequency 13.56MHz-100MHz; Electrode spacing is 5mm-25mm.
The technological parameter of said deposition micro crystal silicon n layer is: reacting gas is silane, hydrogen and phosphine, and wherein hydrogen diluted silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2]))≤20%, phosphorous gas is phosphorus dopant concentration of volume percent PS≤5% with the ratio of silane, reacting gas pressure (0.5-5) Torr; Glow power density (0.1-3) W/cm
2Aura stimulating frequency 13.56MHz-100MHz; Electrode spacing is 5mm-25mm.
The technological parameter of said deposition micro crystal silicon base battery is following:
1) condition of deposition crystallite p layer is: reacting gas is silane, hydrogen and borine, trimethyl borine or boron trifluoride, and wherein hydrogen diluted silane concentration of volume percent SC is [SiH
4]/[SiH
4+ H
2]≤5%, boron-containing gas are boron dope agent concentration of volume percent BS≤5%, reacting gas pressure 0.5-10Torr, glow power density (0.1-3) W/cm with the ratio of silane
2, aura stimulating frequency 13.56MHz-100MHz, electrode spacing be 10mm-25mm;
2) condition of deposition crystallite i layer is: reacting gas is silane, germane or fluoridizes germanium and hydrogen that wherein hydrogen diluted silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2]))≤15%, hydrogen dilution germane concentration of volume percent GC is ([GeH
4]/([GeH
4]+[H
2]))≤15%, it is ([GeF that germanium concentration of volume percent GC is fluoridized in the hydrogen dilution
4]/([GeF
4]+[H
2]))≤15%; Reacting gas pressure (0.5-10) Torr, glow power density (0.1-3) W/cm
2, aura stimulating frequency 13.56MHz-100MHz, electrode spacing be 5mm-25mm;
3) condition of deposited amorphous n layer is: reacting gas is silane, hydrogen and phosphine, wherein hydrogen diluted silane concentration of volume percent SC=([SiH
4]/([SiH
4]+[H
2])) %≤50%, phosphorous gas is phosphorus dopant concentration of volume percent PS≤5% with the ratio of silane; Reacting gas pressure (0.5-5) Torr, glow power density (0.1-3) W/cm
2, aura stimulating frequency 13.56MHz-100MHz, electrode spacing be 5mm-25mm.
Operation principle of the present invention:
The present invention is directed to industrialization cheaply single chamber amorphous silicon-based film solar cell carry out technology upgrading; Propose to adopt hydrogen plasma etching battery amorphous silicon n layer; Deposit crystallite n layer then, battery at the bottom of the last deposition micro crystal silicon, thus form the technology of tying the laminate film batteries more.This technological basic principle is: adopt hydrogen plasma to handle the oxide that etches away battery amorphous silicon n laminar surface; The crystallite P layer of battery forms good tunnel junctions at the bottom of deposition micro crystal silicon n layer and the microcrystal silicon then, to widen the conversion efficiency that absorption spectrum improves battery.
Advantage of the present invention and good effect: this method is through hydrogen plasma treatment of battery amorphous silicon n laminar surface oxide; Deposit battery at the bottom of crystallite N and the microcrystal silicon then; Do not needing under other gas situation of extra introducing; Can widen the absorption spectrum of battery, obtain high open circuit voltage, improve the conversion efficiency of battery.
Description of drawings
Fig. 1 is the J-V curve chart of amorphous silicon/amorphous silicon laminated battery.
Fig. 2 is to be the J-V curve chart of amorphous silicon/amorphous silicon laminated battery of 5s in the hydrogen plasma processing time.
Fig. 3 is to be the J-V curve chart of amorphous silicon/amorphous silicon/microcrystal silicon stacked battery of 5s in the hydrogen plasma processing time.
Fig. 4 is to be the J-V curve chart of amorphous silicon/amorphous silicon laminated battery of 30s in the hydrogen plasma processing time.
Fig. 5 is to be the J-V curve chart of amorphous silicon/amorphous silicon/microcrystal silicon stacked battery of 30s in the hydrogen plasma processing time.
Fig. 6 is to be the attach most importance to J-V curve chart of doped amorphous silicon/amorphous silicon/microcrystal silicon stacked battery of 30s crystallite N in the hydrogen plasma processing time.
Fig. 7 is to be that 30s crystallite N is the J-V curve chart of the amorphous silicon/amorphous silicon/microcrystal silicon stacked battery of high H dilution in the hydrogen plasma processing time.
Fig. 8 is that crystallite P sedimentation time is the J-V curve chart of amorphous silicon/amorphous silicon/microcrystal silicon stacked battery of 3 minutes.
Fig. 9 is that crystallite P sedimentation time is the J-V curve chart of amorphous silicon/amorphous silicon/microcrystal silicon stacked battery of 2 minutes.
The J-V curve chart of the amorphous silicon/amorphous silicon of the I layer sedimentary condition that Figure 10 is different/microcrystal silicon stacked battery.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment technical scheme of the present invention is carried out detailed explanation.
The present invention upgrades to amorphous silicon (or amorphous silicon germanium)/crystalline/micro-crystalline silicon laminated solar battery or amorphous silicon/amorphous silicon (or amorphous silicon germanium)/microcrystal silicon three knot stacked solar cell, cascade solar cells with the single chamber PECVD systems produce amorphous silicon film solar battery of the single-ended introducing of reacting gas of industrialization.This invention can obtain the solar cell of high open circuit voltage, and the conversion efficiency of battery is improved.
Amorphous silicon/amorphous silicon laminated battery of buying with the ability company production line from Tianjin below is that example explains that the present invention proposes the micro crystal silicon solar battery of this battery and narrow band gap is formed the method for the technology upgrading of multijunction solar cell, improves the photoelectric conversion efficiency of battery.The performance parameter of the battery of can company from Tianjin directly buying on the production line is: short-circuit current density (Jsc)=5.12mA/cm
2, open circuit voltage (Voc)=1.681V, fill factor, curve factor (FF)=0.739, efficient (Efficiency)=6.36% (see figure 1).
At first provide two different hydro Cement Composite Treated by Plasma technology.
Embodiment 1:
The condition that a kind of hydrogen plasma is handled is: hydrogen flowing quantity is 190SCCM in the reaction gas, and the reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 5s.Deposit crystallite n layer subsequently, reaction condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.8%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane; Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Resulting battery behavior is as shown in Figure 2: short-circuit current density (Jsc)=6.63mA/cm
2, open circuit voltage (Voc)=1.65V, fill factor, curve factor (FF)=0.66, efficient (Efficiency)=7.22%, efficient has improved 13.5%.Battery at the bottom of deposition micro crystal silicon on the basis of this battery at first deposits crystallite P layer, and reaction condition is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time 2.5 minutes.Deposit crystallite i layer then, reaction condition is: silane flow rate is 16SCCM, and hydrogen flowing quantity is 360SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 4.37%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.88W/cm
2, the aura stimulating frequency is 75MHz, feeds the method for silane behind the earlier logical hydrogen aura of employing, sedimentation time 80 minutes.Last deposited amorphous n layer, reaction condition is following: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.The characteristic of the three knot laminated cells that obtain is as shown in Figure 3: short-circuit current density (Jsc)=5.72mA/cm
2, open circuit voltage (Voc)=1.99V, fill factor, curve factor (FF)=0.68, efficient (Efficiency)=7.72%, efficient has improved 21.4%.
Embodiment 2:
A kind of hydrogen plasma treatment conditions are: hydrogen flowing quantity is 190SCCM in the reaction gas, and the reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit the crystallite n layer the same with last a kind of method subsequently, reaction condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.8%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.The characteristic of resulting battery is as shown in Figure 4: short-circuit current density (Jsc)=6.81mA/cm
2, open circuit voltage (Voc)=1.68V, fill factor, curve factor (FF)=0.65, efficient (Efficiency)=7.37%, efficient has improved 15.9%.Battery at the bottom of deposition micro crystal silicon on the basis of this battery.At first deposit crystallite P layer, reaction condition is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time 2.5 minutes.Deposit crystallite i layer then, reaction condition is: silane flow rate is 16SCCM, and hydrogen flowing quantity is 360SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 4.37%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.88W/cm
2, the aura stimulating frequency is 75MHz, feeds the method for silane behind the earlier logical hydrogen aura of employing, sedimentation time 80 minutes.Last deposited amorphous n layer, reaction condition is following: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.The characteristic of the three knot laminated cells that obtain is as shown in Figure 5: short-circuit current density (Jsc)=5.51mA/cm
2, open circuit voltage (Voc)=2.12V, fill factor, curve factor (FF)=0.72, efficient (Efficiency)=8.44%, efficient has improved 32.7%.
Provide the deposition technique of two different crystallite n layers below.
Embodiment 3:
At first carry out hydrogen plasma and handle, reaction condition is: hydrogen flowing quantity is 190SCCM in the reaction gas.Reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit crystallite n layer then, sedimentary condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 10SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.7%, phosphorous gas is phosphorus dopant concentration of volume percent 1.4% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Then, battery at the bottom of deposition micro crystal silicon on the basis of this battery.At first deposit crystallite P layer, reaction condition is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time 2.5 minutes.Deposit crystallite i layer then, reaction condition is: silane flow rate is 16SCCM, and hydrogen flowing quantity is 360SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 4.37%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.88W/cm
2, the aura stimulating frequency is 75MHz, feeds the method for silane behind the earlier logical hydrogen aura of employing, sedimentation time 80 minutes.Last deposited amorphous n layer, reaction condition is following: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.The characteristic of the three knot laminated cells that obtain is as shown in Figure 6: short-circuit current density (Jsc)=5.32mA/cm
2, open circuit voltage (Voc)=2.05V, fill factor, curve factor (FF)=0.73, efficient (Efficiency)=7.93%, efficient has improved 24.7%.
Embodiment 4:
At first carry out hydrogen plasma and handle, reaction condition is: hydrogen flowing quantity is 190SCCM in the reaction gas.Reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit crystallite n layer then, sedimentary condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 190SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.4%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura driving frequency is 75MHz.Sedimentation time is 3.25 minutes.Then, battery at the bottom of deposition micro crystal silicon on the basis of this battery.At first deposit crystallite P layer, reaction condition is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time 2.5 minutes.Deposit crystallite i layer then, reaction condition is: silane flow rate is 16SCCM, and hydrogen flowing quantity is 360SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 4.37%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.88W/cm
2, the aura stimulating frequency is 75MHz, feeds the method for silane behind the earlier logical hydrogen aura of employing, sedimentation time 80 minutes.Last deposited amorphous n layer, reaction condition is following: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.The characteristic of the three knot laminated cells that obtain is as shown in Figure 7: short-circuit current density (Jsc)=5.59mA/cm
2, open circuit voltage (Voc)=1.99V, fill factor, curve factor (FF)=0.68, efficient (Efficiency)=7.53%, efficient has improved 18.4%.
Provide the deposition technique of the P layer of battery at the bottom of two different microcrystal silicons below.
Embodiment 5:
At first carry out hydrogen plasma and handle, reaction condition is: hydrogen flowing quantity is 190SCCM in the reaction gas.Reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit crystallite n layer then, reaction condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.8%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane; Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Battery at the bottom of the deposition micro crystal silicon again, the sedimentary condition of its P layer is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz.Sedimentation time is 3 minutes.Deposit crystallite i layer then, reaction condition is: silane flow rate is 16SCCM, and hydrogen flowing quantity is 360SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 4.37%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.88W/cm
2, the aura stimulating frequency is 75MHz, feeds the method for silane behind the earlier logical hydrogen aura of employing, sedimentation time 80 minutes.Last deposited amorphous n layer, reaction condition is following: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.The characteristic of the three knot laminated cells that obtain is as shown in Figure 8: short-circuit current density (Jsc)=5.60mA/cm
2, open circuit voltage (Voc)=2.07V, fill factor, curve factor (FF)=0.70, efficient (Efficiency)=8.10%, efficient has improved 27.3%.
Embodiment 6:
At first carry out hydrogen plasma and handle, reaction condition is: hydrogen flowing quantity is 190SCCM in the reaction gas, and the reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit crystallite n layer then, sedimentary condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.8%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane; Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Battery at the bottom of the deposition micro crystal silicon again.The sedimentary condition of P layer is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz.Sedimentation time is 2 minutes.Deposit crystallite i layer then, reaction condition is: silane flow rate is 16SCCM, and hydrogen flowing quantity is 360SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 4.37%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.88W/cm
2, the aura stimulating frequency is 75MHz, feeds the method for silane behind the earlier logical hydrogen aura of employing, sedimentation time 80 minutes.Last deposited amorphous n layer, reaction condition is following: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.The characteristic of the three knot laminated cells that obtain is as shown in Figure 9: short-circuit current density (Jsc)=5.01mA/cm
2, open circuit voltage (Voc)=2.08V, fill factor, curve factor (FF)=0.68, efficient (Efficiency)=7.10%, efficient has improved 11.6%.
Provide battery i layer deposition techniques at the bottom of two different microcrystal silicons below.
Embodiment 7:
At first carry out hydrogen plasma and handle, reaction condition is: hydrogen flowing quantity is 190SCCM in the reaction gas, and the reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit crystallite n then, reaction condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.8%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane; Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Deposit crystallite P layer then, reaction condition is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Deposit crystallite i again, deposit the n layer at last, its sedimentary condition is: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.Wherein the sedimentary condition of i layer is that silane flow rate is 20.3SCCM, and hydrogen flowing quantity is 329.7SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 5.8%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.63W/cm
2, the aura driving frequency is 75MHz.The characteristic corresponding silane concentration SC=5.8% shown in figure 10 of the three knot laminated cells that obtain): short-circuit current density (Jsc)=5.38mA/cm
2, open circuit voltage (Voc)=2.12V, fill factor, curve factor (FF)=0.70, efficient (Efficiency)=7.99%, efficient has improved 25.6%.
Embodiment 8:
At first carry out hydrogen plasma and handle, reaction condition is: hydrogen flowing quantity is 190SCCM in the reaction gas, and the reaction pressure in the reaction chamber remains on 0.7Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, aura 30s.Deposit crystallite n then, reaction condition is: silane flow rate is 7SCCM, and hydrogen flowing quantity is 170SCCM, and the phosphine flow is 7SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 3.8%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane; Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.45W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Deposit crystallite P layer then, reaction condition is: silane flow rate is 2SCCM, and hydrogen flowing quantity is 170SCCM, and the borine flow is 10SCCM (dilution of 0.1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 1.1%, boron-containing gas is a boron dope agent concentration of volume percent 0.5% with the ratio of silane; Reaction pressure in the reaction chamber remains on 2.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.5W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 3 minutes.Deposit crystallite i again, deposit the n layer at last, sedimentary condition is: silane flow rate is 15SCCM, and hydrogen flowing quantity is 85SCCM, and the phosphine flow is 15SCCM (dilution of 1% hydrogen), and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 15%, phosphorous gas is phosphorus dopant concentration of volume percent 1% with the ratio of silane.Reaction pressure in the reaction chamber remains on 1.5Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.375W/cm
2, the aura stimulating frequency is 75MHz, sedimentation time is 2 minutes.Wherein the sedimentary condition of i layer is that silane flow rate is 21SCCM, and hydrogen flowing quantity is 329SCCM, and corresponding silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2])) 6%; Reaction pressure in the reaction chamber remains on 1.8Torr, and hot trap heating-up temperature remains on 280 ℃, sets glow power 0.63W/cm
2, the aura stimulating frequency is 75MHz.The characteristic (corresponding silane concentration SC=6%) shown in figure 10 of the three knot laminated cells that obtain: short-circuit current density (Jsc)=5.58mA/cm
2, open circuit voltage (Voc)=2.14V, fill factor, curve factor (FF)=0.70, efficient (Efficiency)=8.33%, efficient has improved 31%.
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 (1)
1. method that improves industrialization deposited in single chamber amorphous silicon-based film battery efficiency; It is characterized in that: the amorphous silicon-based film solar cell of industrialization deposited in single chamber and the microcrystalline silicon solar cell of narrow band gap are formed many knot stacked solar cell, cascade solar cells; Np tunnel junctions to the centre is carried out technological design; Form heavily doped doped layer and good tunnelling characteristic, concrete steps are following:
1) the amorphous silicon n layer of the amorphous silicon-based film solar cell through hydrogen plasma process etching industrialization deposited in single chamber, technological parameter is: reacting gas is a hydrogen, and reacting gas pressure is greater than 0.5Torr; Glow power density (0.1-3) W/cm
2Aura stimulating frequency 13.56MHz-100MHz; Electrode spacing is 5mm-25mm;
2) then through plasma process deposition micro crystal silicon n layer, technological parameter is: reacting gas is silane, hydrogen and phosphine, and wherein hydrogen diluted silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2]))≤20%, phosphorous gas is phosphorus dopant concentration of volume percent PS≤5% with the ratio of silane, reacting gas pressure (0.5-5) Torr; Glow power density (0.1-3) W/cm
2Aura stimulating frequency 13.56MHz-100MHz; Electrode spacing is 5mm-25mm;
3) at last through plasma process deposition micro crystal silicon base battery, technological parameter is following:
⑴ the condition of, deposition crystallite p layer is: reacting gas is silane, hydrogen and borine, trimethyl borine or boron trifluoride, and wherein hydrogen diluted silane concentration of volume percent SC is [SiH
4]/[SiH
4+ H
2]≤5%, boron-containing gas are boron dope agent concentration of volume percent BS≤5%, reacting gas pressure 0.5-10Torr, glow power density (0.1-3) W/cm with the ratio of silane
2, aura stimulating frequency 13.56MHz-100MHz, electrode spacing be 10mm-25mm;
⑵ the condition of, deposition crystallite i layer is: reacting gas is silane, germane or fluoridizes germanium and hydrogen that wherein hydrogen diluted silane concentration of volume percent SC is ([SiH
4]/([SiH
4]+[H
2]))≤15%, hydrogen dilution germane concentration of volume percent GC is ([GeH
4]/([GeH
4]+[H
2]))≤15%, it is ([GeF that germanium concentration of volume percent GC is fluoridized in the hydrogen dilution
4]/([GeF
4]+[H
2]))≤15%; Reacting gas pressure (0.5-10) Torr, glow power density (0.1-3) W/cm
2, aura stimulating frequency 13.56MHz-100MHz, electrode spacing be 5mm-25mm;
⑶ the condition of, deposited amorphous n layer is: reacting gas is silane, hydrogen and phosphine, wherein hydrogen diluted silane concentration of volume percent SC=([SiH
4]/([SiH
4]+[H
2]))≤50%, phosphorous gas is phosphorus dopant concentration of volume percent PS≤5% with the ratio of silane; Reacting gas pressure (0.5-5) Torr, glow power density (0.1-3) W/cm
2, aura stimulating frequency 13.56MHz-100MHz, electrode spacing be 5mm-25mm.
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