GB2471128A - Surface passivation of silicon wafers - Google Patents
Surface passivation of silicon wafers Download PDFInfo
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- GB2471128A GB2471128A GB0910568A GB0910568A GB2471128A GB 2471128 A GB2471128 A GB 2471128A GB 0910568 A GB0910568 A GB 0910568A GB 0910568 A GB0910568 A GB 0910568A GB 2471128 A GB2471128 A GB 2471128A
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- Prior art keywords
- silicon nitride
- doped
- silicon
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- thickness
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- 238000002161 passivation Methods 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 239000010703 silicon Substances 0.000 title claims abstract description 29
- 235000012431 wafers Nutrition 0.000 title 1
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 72
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000151 deposition Methods 0.000 claims abstract description 39
- 239000007789 gas Substances 0.000 claims abstract description 39
- 230000008021 deposition Effects 0.000 claims abstract description 31
- 239000004065 semiconductor Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002019 doping agent Substances 0.000 claims abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 9
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 claims description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims 4
- 230000000694 effects Effects 0.000 abstract description 17
- 239000012535 impurity Substances 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000003071 parasitic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004050 hot filament vapor deposition Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 2
- 238000000995 aerosol-assisted chemical vapour deposition Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000259 microwave plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910005091 Si3N Inorganic materials 0.000 description 1
- -1 SiCI2H2 Chemical compound 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000663 remote plasma-enhanced chemical vapour deposition Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000038 ultrahigh vacuum chemical vapour deposition Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
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- 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
- H01L21/02112—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 characterised by the material of the layer
- H01L21/02123—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 characterised by the material of the layer the material containing silicon
- H01L21/0217—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 characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C23C16/303—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- C—CHEMISTRY; METALLURGY
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/318—Inorganic layers composed of nitrides
- H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides
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- 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
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
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- 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
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/50—Photovoltaic [PV] energy
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- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
A method of producing wafer based solar panels, whereby the cells obtain an improved field passivation effect. A method for passivation of a surface comprises placing the silicon semiconductor in the deposition chamber of a dielectric chemical vapour deposition equipment, introducing precursor gases for forming a silicon nitride film on the exposed surface of the silicon semiconductor into the deposition chamber, initiating deposition of a silicon nitride film on the silicon semiconductor, doping the deposited silicon nitride film by introducing at least one gaseous compound containing an element which acts as an acceptor element into the precursor gases in the deposition chamber, and continuing depositing the silicon nitride film until the film obtains a thickness in the range of 2 - 500 nm. Preferably the acceptor dopant is boron. The invention also relates to solar cells comprising p-doped silicon nitride passivation layers produced by a similar method, whereby the silicon nitride film has an impurity density of between 109and 1015cm-2.
Description
I
Method for improved passivation and solar cell with improved passivation This invention relates to a production method of wafer based solar panels, and which the cells obtain an improved field passivation effect and solar cells with
improved field passivation effects.
Background
The world supplies of fossil oi1 are expected to be gradually exhausted in the following decades. This means that our main energy source for the last century will have to be replaced within a few decades, both to cover the present energy consumption and the coming increase in the global energy demand.
In addition, there are raised many concerns that the use of fossil energy is increasing the earth greenhouse effect to an extent that may turn dangerous. Thus the present consumption of fossil fuels should preferably be replaced by energy sources/carriers that are renewable and sustainable for our climate and environment.
One such energy source is solar light, which irradiates the earth with vastly more energy than the present and any foreseeable increase in human energy consumption. However, solar cell electricity has up to date been too expensive to be competitive with present grid power made by nuclear power, thermal power etc. This needs to change if the vast potential of the solar cell electricity is to be realised.
The cost of electricity from a solar panel is a function of the energy conversion efficiency and the production costs of the solar panel. Obviously, the search for cheaper solar electricity should thus be focused at high-efficient solar cells made by cost-effective manufacturing methods. Presently, the main production of solar cells is based on silicon as the photovoltaic material, and silicon based solar cells are expected to be the mainstay in the foreseeable future.
One important factor for enhancing the energy conversion efficiency of solar cells is electric insulation of the surface of the semiconductor. This is known as surface passivation of the solar cell, and is obtained by depositing one or more layers of a dielectric in order to reduce/avoid recombination of charge carriers at the interface between the deposited dielectric surface and semiconductor.
Silicon nitride films have seen more and more use as surface passivation layer in high-efficient solar cells due to the favourable combination of excellent passivation effect and anti-reflection effect. A further advantage of the silicon nitride film is that it may relatively easy and cost-effectively be deposited in industrially applicable manufacturing processes by use of chemical vapour deposition (CVD).
Prior art
Recently, the trend of employing thinner crystalline silicon solar cells has created a need for effective low-cost rear surface passivation due to the cell thickness reaching dimensions of the same order as the diffusion lengths of the charge carriers.
According to Dauwe et a!. [1], amorphous hydrogenated silicon nitride (SiNs) films deposited on low-resistivity p-doped crystalline silicon by low temperature (<400 °C) plasma-enhanced chemical vapour deposition (PECVD) have been shown to give very low recombination velocities (SRVs), and is thus a promising candidate for low-cost rear surface passivation films.
The low surface recombination velocities of Si/SiNs interfaces are probably due to two different reasons. The first reason is saturation of dangling bonds at the interface by atomic hydrogen released from the precursor gases (SilL1 and NH3), giving an effect due to decreased interface state density. The second reason is due to fixation of a high density of positive charges in the deposited SiNg-films, giving rise to a field-effect passivation. According to Weber and Jin [2], the fixation of positive charges in PECVD deposited SiNs-films is due to an over-stochiometric ratio of silicon in the precursor gases during the deposition of the film, typically giving a density of positive charge in the film in the order of 1012 cm2. The silane is decomposed into positively charged ions (cationic gas) and ammonia is decomposed into negatively charged ions (anionic gas).
However, when SiNg-films with excess of positive fixed charges are applied OIl p-doped semiconductors, the field effect of the positive charges will serve to withhold/fix negative charges at the surface boundary region of the semiconductor and thus create a negatively charged layer underneath the SiNs-film. This layer is known as an inversion layer. The inversion layer in p-doped semiconductors is known to create problems at the metal contacts on the back/rear of the cells, due to a short circuit effect in the vicinity of the electrode which reduces the collected current of the rear side of the solar cell.. This short circuiting effect is known as parasitic shunting.
Dauwe et al. [1] performed experiments on 1.5 Qcm FZ p-type silicon cells illuminated by AM1.5G 100 mW/cm2 at 25 °C. The tests were made for cells provided with a Si02 rear side passivation film and compared the cells energy conversion efficiency with similar cells provided with a PECVD deposited SiNs rear side passivation film. They found that the parasitic shunting effect reduced the cell energy conversation efficiency from 17.9 percent points with Si02-passivation film to 16.8 percent points with S1NX passivation film, a loss of 6.2 %. They showed further that by inserting a silicon oxide zone in the SiNX rear side passivation layer acting to electrically insulating the rear side electric contacts from the inversion layer, the parasitic shunting effect was almost eliminated giving a cell efficiency of 17.8 percent points.
US 2007/0186970 discloses use of a catalytic chemical vapours deposition process to form the silicon nitride passivation film. According to the document, there is in this process no problem with high-energy charged particles causing damage in the surface boundary of the semiconductor substrate, as is the case for plasma-enhanced chemical vapour deposition, or of degradation of the passivation film due to inclusion of charged particles.
Hoex et al. [3] shows from lifetime measurements, including a direct experimental comparison with thermal Si02, a-Si:H, and as-deposited a-SiNx:H, that A1203, which contains negative charges, provides an excellent level of surface passivation on highly B-doped c-Si with doping concentrations around 1019 cm3. The Al203 films, synthesized by plasma-assisted atomic layer deposition and with a high fixed negative charge density, limit the emitter saturation current density of B-diffused p+-emitters to 10 and -30 fAJcm2 on >100 and 54 cl/sq sheet resistance p+-emitters, respectively. These results demonstrate that highly doped p-type Si surfaces can be passivated effectively with negatively charged films.
WO 02/4 1408 discloses a method for removing the inversion layer in rear surface Si02 passivated cells by depositing a fluoride layer with negative charges onto the Si02-film.
Weber and Jin [2] teaches a method where a corona discharge is used to create and store negative charge in the silicon nitride films of silicon dioxide/silicon nitride stacks. Effective lifetime measurements on both textured and planar, as well as both boron diffused and non-diffused silicon samples passivated with silicon oxide/silicon nitride stacks, show that the creation of negative charge in the nitride layer results in an improvement in the surface passivation for all samples, with very low (<2 cm/s) effective surface recombination velocities demonstrated for planar, non-diffused samples. The manipulation of charge can be exploited to improve the conversion efficiency of silicon solar cells.
Objective of the invention The main objective of the invention is to provide a cost effective industrially applicable method for passivation of silicon based solar cells, and where the passivation effect provides effective surface recombination velocities of less than cm/s.
The objective of the invention may be realised by the features as set forth in the description of the invention below, and/or in the appended patent claims.
Description of the invention
The invention is based on the realisation that a cost effective industrial applicable method of forming a passivation film with similar excellent passivation properties as the passivation films with negative charge in the prior art above, may be obtained if the negative charge in the passivation layer may be introduced during presently industrially employed deposition processes based on chemical vapour deposition.
Thus in a first aspect, the present invention relates to a method for surface passivation of a silicon semiconductor, where the method comprises: -placing the silicon semiconductor in the deposition chamber of a dielectric chemical vapour deposition equipment, -introduce precursor gases for forming a silicon nitride film on the exposed surface of the silicon semiconductor into the deposition chamber, -initiate deposition of a silicon nitride film on the silicon semiconductor, -doping the deposited silicon nitride film by introducing at least one gaseous compound containing an element which acts as an acceptor element into the precursor gases in the deposition chamber, and -continue depositing the silicon nitride film until the film obtains a thickness in the range of 2-500 nm.
Thus the first aspect of the invention obtains introduction of negative charges in the passivation film (silicon nitride film) by introducing atoms which functions as electron acceptors in the silicon nitride film. Negative charges in the silicon nitride film will withhold positive charges on the wafer surface; in just the same manner as positive charges in the passivation film withholds negative charges and creates the inversion layer. The positive charges on the surface of the p-type doped wafer will have a beneficial effect on the solar cell structure by providing an increased field passivation effect. The layer of positive charges in the surface region of the semiconductor wafer may be considered as an inversed inversion layer, or an accumulation layer, and will be denoted "the positive charged layer" in this application.
In a second aspect, the invention relates to solar cells, where the solar cells comprises: -a silicon semiconductor wafer or film where at least on the front or rear surface, alternatively both surfaces, have at least one layer of silicon nitride deposited by chemical vapour deposition, -the silicon nitride film contains an element which acts as an acceptor element in the film and thus form negatively charged film, and where -the concentration of dopants in the silicon nitride film results in a negative charge of the film in the range from i09 and 1015 cm2.
The invention will practically eliminate the parasitic shunting effect and obtain the beneficial combined effect of the excellent chemical passivation effect of the silicon nitride film and the field passivation effect of the fixed positive layer.
Another advantage is that this effect may be obtained by employing presently implemented infrastructure for deposition of passivation films in the photovoltaic industry, and thus constituting a very cost effective solution to the problem of parasitic shunting which may relatively easily be implemented in existing production lines.
The term "acceptor" as used herein means any dopant atom added to the silicon nitride film which can contribute to form a negatively charged film. The formation of negatively charged regions in the film is believed to be due to substitution of a silicon atom in the silicon nitride film with a dopant atom which has at least one less valence electron than the silicon atom. This substitution will result in formation of one or more molecular orbitals in one neighbouring silicon atom in the film with an electron vacancy, and this unsatisfied bond will extract an electron from the surroundings and thus form a silicon atom in the film with a net negative charge and thus form the negatively charged regions of the film.
Boron and aluminium are examples of suitable dopants.
The entire silicon nitride film may be doped by simply mixing the silicon nitride forming precursor gases with the dopant forming gas (for instance a boron or aluminium containing gas) in the deposition chamber during the entire deposition of the silicon nitride film. It also envisioned forming only a doped layer into the silicon nitride film. This may be obtained by introducing the dopant gases into the deposition chamber for only a period of the deposition process. The thickness of the doped layer and the dopant density in the layer may be controlled by regulating the time period when the dopant gases are introduced into the deposition chamber and the concentration of the dopant gases in the deposition chamber of the dielectric deposition equipment, respectively.
The invention may apply any known or conceivable chemical vapour deposition technique known to be able to form a silicon nitride film. Suitable deposition techniques includes, but are not limited by, Atmospheric pressure CVD (APCVD), Low-pressure CVD (LPCVD), Ultrahigh vacuum C\'D (UHVCVD), Aerosol assisted CVD (AACVD), Microwave plasma-assisted CVD (MPCVD), Plasma-Enhanced CVD (PECVD), Remote plasma-enhanced C\TD (RPECVD), Atomic layer CVD (ALCVD), Hot wire CVD (HWCVD), Catalytic CVD (Cat-CVD), hot filament CVD (HFCVD).
The invention may apply any known or conceivable precursor gas able to form silicon nitride by chemical vapour deposition. Examples of suitable precursor gases includes, but are not limited by, S1H4, SiCI2H2, N2, and NH3. The chemical reactions involved may be given as: 3SiH4 + 4NH3 -b Si3N + 12H2 3SiCl2H2 + 4NH3 -p Si3N4 + 6HCI + 6H2 2SiH4+N2 -2SiNH+ 3H2 SiH4 +NH3 -SINH + 3H2 The dopant forming gases may be any chemical compound which is in the gas phase at the conditions experienced in the deposition chamber of chemical vapour deposition equipment, and which contains an element from group III of the periodic table. The compound should preferably be a nitride or a hydride of the group III element in order to avoid introducing "foreign" or in any way polluting elements into the deposition chamber. Diborane, B2H6, is an example of such a compound, and which is suitable for forming the p-type doped silicon nitride film according to the first aspect of the invention.
The silicon nitride layer may be applied as a second or third dielectric layer. That is, the silicon semiconductor may be provided with one or two dielectric layer(s) before depositing the silicon nitride layer (including the doped silicon nitride layer).
The inventive idea of employing a dopant forming gas in the deposition chamber which provides a negatively charged silicon nitride film may also be applied to other dielectric films than silicon nitride. In this case the precursor gases forming the dielectric film are admixed with a dopant gas in the same manner as the precursor gases forming the silicon nitride film. The use of other negatively doped dielectric films may also be combined with the silicon nitride film according to the first or second aspect of the invention.
One example of a high efficient and much employed dielectric film on silicon based solar cells is silicon dioxide, Si02. Silicon dioxide may be applied by chemical vapour deposition using silane and oxygen at temperature in the deposition chamber between 50 -500 °C. It is also possible to employ dichlorosilane, SiCI2H2, nitrous oxide, N20, or an organic silicon compound.
Possible chemical reactions are: SiH4 + 02 -Si02 + 2H2 SiC12H2 + 2N20 -Si02 + 2N2 + 2HC1 By mixing a gas containing an element which acts as acceptor in the silicon dioxide film into the precursor gases, it is obtained a negatively charged silicon dioxide dielectric film which will form an accumulator layer in the surface region of the silicon semiconductor. The dopant forming gas may i.e. be B2H6.
Typical thickness of the doped silicon oxide film will be from 10 to 200 nm, but may also be outside this range.
The invention may apply any conceivable dielectric film suited to be used as surface passivation on silicon semiconductors and which may be deposited by chemical vapour deposition.
It is envisioned that the silicon dioxide passivation film may be applied as the only passivation film or in combination with the silicon nitride layer of the first and second aspect of the invention. The use of doped silicon dioxide may be obtained by simply substitute the NH3 or N2 precursor gas with 02 or N20 during deposition of the dielectric layer.
Another example of suited dielectric layer is hydrogenated amorphous silicon, a-H: Si, which may be formed by chemical vapour deposition of silane gas at a temperature in the deposition chamber of 50 -500 °C: SiFL1 -a-H:Si + 2H2 The film may be doped by introduction of a boron containing gas, i.e. diborane, B2H6. It is envisioned that the hydrogenated silicon film may be used in combination with silicon dioxide, silicon nitride or both. Typical thickness of the doped hydrogenated amorphous silicon film will be from 2 to 200 nm, but may also be outside this range.
Example embodiment
An example embodiment of a solar cell made according to the invention is presented in Figure 1.
The Figure shows a silicon semiconductor wafer 1 which is doped to form a front side layer 2 of n-type doping and a rear side layer 3 of p-type doping. The front side is provided with one dielectric layer 4 of silicon nitride and a grid of front side electric contacts 5 establishing electric contact with the n-type doped layer 2.
The rear side is provided with a first dielectric layer 6 of silicon dioxide and a second dielectric layer 7 of silicon nitride. The back side is provided with a metallic layer 8 forming the back side electric contact. The electric contact 8 is made with protrusions 9 which locally extend through the dielectric layers in order to make contact with the p-type doped layer 3.
An inversion layer 10 is also indicated in the Figure. In case of prior art which employs a non-doped silicon nitride dielectric layer 7, the inversion layer will be negatively charged and will thus result in parasitic shunting due to contact with the positive contact 9. However, by employing a doped silicon nitride layer 7 according to this invention, the inversion layer 10 will be inversed to form an accumulation layer which increases the current density of the solar cell. The contact between an accumulation layer 10 and electric contact 9 is no longer a problem, it is an asset.
The silicon nitride dielectric layer 7 is deposited by use of plasma enhanced chemical vapour deposition by use of SiH4 and NH3 as precursor gases admixed with B2H6. The deposition process is run at a temperature in the deposition chamber in the range from 250 to 450°C, and the process is run until a thickness of the silicon nitride dielectric layer 7 is in the range between 40-200 nm is obtained.
References 1 Stefan Dauwe et al. (2002), "Experimental evidence of Parasitic Shunting in Silicon Nitride Rear Surface Passivated Solar Cells", Frog. Photovolt: Res.Appl., 10:271-278.
2 Weber and Jin (2009), "Improved silicon surface passivation achieved by negatively charged silicon nitride films", Applied Physics Letters, 94, 063509 3 Hoex et al. (2007), "Excellent passivation of highly doped p-type Si surfaces by the negative-charge-dielectric A1203", Applied Physics Letters, 91, 112107
Claims (15)
- CLAIMS1. Method for surface passivation of a silicon semiconductor, where the method comprises: -placing the silicon semiconductor in the deposition chamber of a dielectric chemical vapour deposition equipment, -introduce precursor gases for forming a silicon nitride film on the exposed surface of the silicon semiconductor into the deposition chamber, -initiate deposition of a silicon nitride film on the silicon semiconductor, -doping the deposited silicon nitride film by introducing at least one gaseous compound containing an element which acts as an acceptor element into the precursor gases in the deposition chamber, and -continue depositing the silicon nitride film until the film obtains a thickness in the range of 2-500 nm.
- 2. Method according to claim 1, where -the dielectric layer is deposited by use of plasma-enhanced chemical vapour deposition.
- 3. Method according to claim 2, where -the precursor gases are SiH4 and NH3, -the temperature in the deposition chamber is kept between 50 -500 °C, and -the dopant forming gas is a gaseous compound containing boron.
- 4. Method according to claim 3 where -the precursor gases are SiH4 and one of N20 or an organic silicon containing precursor and 02, -the temperature in the deposition chamber is kept between 50 -500 °C, and -the dopant forming gas is a gaseous compound containing boron.
- 5. Method according to claim 3 or 4, where dopant forming gas is B2H6.
- 6. Method according to claim 5, where -the temperature in the deposition chamber is kept between 250 -400 °C, and -the thickness of the deposited film is in the range of 40 -200 nm.
- 7. Method according to any of the preceding claims, where the also comprises -forming a first dielectric layer onto the semiconductor of amorphous silicon or silicon dioxide, and then -depositing the silicon nitride layer as the second dielectric layer.
- 8. Method according to claim 7, where the deposition of the dielectric layer is performed by -employing SiH4 and one of N20 or an silicon containing organic precursor and 02 as precursor gases to form a first dielectric layer of Si02 on the semiconductor, then -employing SiH4, NH3, and B206 as precursor gases to form a p-type doped silicon nitride layer onto the first dielectric layer, and then -employing SiH4 and NH3 as precursor gases to form a non-doped silicon nitride layer onto the p-typed doped silicon nitride layer.
- 9. Solar cell, comprising: -a silicon semiconductor wafer or film where at least on the front or rear surface, alternatively both surfaces, have at least one layer of silicon nitride, -the silicon nitride film contains an element which acts as an acceptor element in the film and thus form a p-type doped region, and where -the concentration of p-type doped regions in the silicon nitride film results in a negative charge of the film in the range from and 1015 cm2.
- 10. Solar cell according to claim 9, where -the at least one deposited dielectric film is a silicon nitride film of thickness 2 - 500 nm, and -which contains elemental boron in a concentration providing a negative charge density in the range from and 1015 cm2.
- 11. Solar cell according to claim 9, where the semiconductor wafer contains -a first dielectric layer of amorphous silicon or silicon dioxide with thickness of 2 -500 nm, -a doped silicon nitride layer onto the first dielectric layer, which have thickness in the range of 10 -200 nm and which is doped with boron in a concentration providing a negative charge density in the range from i09 and i0 cm2, and -a final non-doped silicon nitride layer onto the doped SiliCon nitride layer, and which has thickness in the range from 2 -500 nm.
- 12. Solar cell according to claim 9, where the semiconductor wafer contains -a first dielectric layer of doped amorphous silicon or doped silicon dioxide with thickness of 2 -500 nm, and which is doped with boron in a concentration providing a negative charge density in the range from i� and 1015 cm2, -a doped silicon nitride layer onto the first dielectric layer, which have thickness in the range of 10 -200 nm and which is doped with boron in a concentration providing a negative charge density in the range from i09 and i0 cm2, and -a final non-doped silicon nitride layer onto the doped silicon nitride layer, and which has thickness in the range from 2 -500 nm.
- 13. Solar cell according to claim 9, where the semiconductor wafer contains -a first dielectric layer of doped amorphous silicon or doped silicon dioxide with thickness of 2 -500 nm, and which is doped with boron in a concentration providing a negative charge density in the range from 1O9 and 1015 cm2, and -a doped silicon nitride layer onto the first dielectric layer, which have thickness in the range of 10 -200 nm and which is doped with boron in a concentration providing a negative charge density in the range from i09 and 1015 cm2.
- 14. Solar cell according to claim 9, where the semiconductor wafer contains -a first dielectric layer of doped amorphous silicon or doped silicon dioxide with thickness of 2 -500 nm, and which is doped with boron in a concentration providing a negative charge density in the range from i09 and 1015 cm2, and -a non-doped silicon nitride layer onto the doped silicon nitride layer, and which has thickness in the range from 2 -500 nm.
- 15. Solar cell according to claim 9, where the semiconductor wafer contains -a first dielectric layer of amorphous silicon with thickness of 2 -200 nm, -a second dielectric layer of silicon dioxide with thickness of 10 -200 nm, and -a third dielectric layer of silicon nitride with thickness of 2 -500 nm, and where -at least one of the first, second or third dielectric layer is doped with boron in a concentration providing a negative charge density in the range from and 1015 cm2.
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WO2015076678A1 (en) * | 2013-11-19 | 2015-05-28 | Institutt For Energiteknikk | Passivation stack on a crystalline silicon solar cell |
US9978902B2 (en) | 2013-11-19 | 2018-05-22 | Institutt For Energiteknikk | Passivation stack on a crystalline silicon solar cell |
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US8841664B2 (en) * | 2011-03-04 | 2014-09-23 | Semiconductor Energy Laboratory Co., Ltd. | Semiconductor device |
CN103117324B (en) * | 2011-11-16 | 2016-07-06 | 中建材浚鑫科技股份有限公司 | A kind of method of back surface passivation and a kind of method making solaode |
CN109545656B (en) * | 2018-10-12 | 2023-05-02 | 南昌大学 | Preparation method of hydrogenated amorphous silicon film |
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WO2006110048A1 (en) * | 2005-04-14 | 2006-10-19 | Renewable Energy Corporation Asa | Surface passivation of silicon based wafers |
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WO2015076678A1 (en) * | 2013-11-19 | 2015-05-28 | Institutt For Energiteknikk | Passivation stack on a crystalline silicon solar cell |
CN105745768A (en) * | 2013-11-19 | 2016-07-06 | 能源技术研究所 | Passivation stack on a crystalline silicon solar cell |
JP2017504186A (en) * | 2013-11-19 | 2017-02-02 | インスティテュート フォー エナジェテクニック | Passivation stack on crystalline silicon solar cells |
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CN105745768B (en) * | 2013-11-19 | 2017-11-24 | 能源技术研究所 | Passivation stack part on crystal silicon solar energy battery |
US9978902B2 (en) | 2013-11-19 | 2018-05-22 | Institutt For Energiteknikk | Passivation stack on a crystalline silicon solar cell |
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