CN107170840A - Back contacts heterojunction solar battery and its emitter stage, solar cell preparation method - Google Patents
Back contacts heterojunction solar battery and its emitter stage, solar cell preparation method Download PDFInfo
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- CN107170840A CN107170840A CN201710369141.4A CN201710369141A CN107170840A CN 107170840 A CN107170840 A CN 107170840A CN 201710369141 A CN201710369141 A CN 201710369141A CN 107170840 A CN107170840 A CN 107170840A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910019923 CrOx Inorganic materials 0.000 claims abstract description 57
- 239000010408 film Substances 0.000 claims description 159
- 229910052710 silicon Inorganic materials 0.000 claims description 59
- 239000010703 silicon Substances 0.000 claims description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 58
- 238000002161 passivation Methods 0.000 claims description 58
- 239000000758 substrate Substances 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 13
- 239000006117 anti-reflective coating Substances 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910021419 crystalline silicon Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000010931 gold Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000006798 recombination Effects 0.000 description 8
- 238000005215 recombination Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002207 thermal evaporation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 238000005137 deposition process Methods 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 210000004508 polar body Anatomy 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
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- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—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
- H01L31/06—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 characterised by potential barriers
- H01L31/072—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/074—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 characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a heterojunction with an element of Group IV of the Periodic Table, e.g. ITO/Si, GaAs/Si or CdTe/Si solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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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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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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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
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Abstract
The present invention relates to technical field of solar cells, a kind of emitter stage of back contacts heterojunction solar battery is disclosed, from top to bottom including at least one layer of CrOxFilm.The invention also discloses a kind of using back contacts heterojunction solar battery of above-mentioned emitter stage and preparation method thereof.The present invention can greatly improve the efficiency of solar cell.
Description
Technical field
The present invention relates to technical field of solar cells, more particularly to a kind of back contacts heterojunction solar battery and its transmitting
Pole, solar cell preparation method.
Background technology
Back contacts hetero-junctions (Heterojunction back contact, abbreviation HBC) solar cell is used as the efficient sun
One kind of battery, its combine interdigitated back contacts (Interdigitated back contat, abbreviation IBC) solar cell with
The advantage of hetero-junctions (Heterojunction with Intrinsic Thin layer, abbreviation HIT) solar cell, Ke Yi great
It is big to improve efficiency of solar cell.
The structure of general HBC solar cells from top to bottom successively include passivation layer, crystal silicon layer, amorphous silicon passivation layer,
Emitter stage and emitter electrode and base electrode.Wherein, the advantage based on IBC solar cells, the preceding surface of HBC solar cells
Also without metal electrode, but the emitter stage and the back of the body of interdigitated configuration are formed in the back surface of silicon chip by mask or photoetching process
Field areas, and corresponding emitter electrode and base electrode are set in emitter stage and back surface field area, so as to avoid because before silicon chip
The shading loss that surface sets metal electrode and caused, improves battery efficiency.And based on the advantage of HIT solar cells, the HBC sun
Battery is the non-crystalline silicon (a-Si by crystalline silicon (c-Si) and heavy doping again:H) the high efficiency cell configuration formed, and in heavy doping
Non-crystalline silicon and crystalline silicon interface introduce one layer of intrinsic amorphous silicon as passivation layer, in this way, can both reduce crystal silicon chip
Body area is combined, and Interface composites can be reduced again, HBC solar cells is had higher open-circuit voltage and short circuit current flow.To sum up, by
Crystalline silicon (c-Si) and the non-crystalline silicon (a-Si of heavy doping:H) the HBC solar cells not only efficiency high, and be also to reach formed
One important channel of crystal-silicon solar cell Efficiency Limit (30%).
Although the battery efficiency of HBC solar cells is high, the emitter stage of HBC solar cells at this stage is by heavily doped
The formation of miscellaneous non-crystalline silicon, and the doped source of non-crystalline silicon is borine or phosphine, inflammable and explosive and severe toxicity, these can all increase
The cost of HBC batteries, hinders the extensive utilization of HBC batteries；At the same time, and with the increase of doping concentration, hair can be increased
Compound (i.e. the surface recombination and auger recombination) of emitter-base bandgap grading, so that the open-circuit voltage of battery is reduced, and the reduction of battery open circuit voltage
Also it further limit the lifting of battery efficiency so that the efficiency of HBC solar cells can not obtain higher lifting.
The content of the invention
In order to solve the above problems, the present invention provides a kind of back contacts heterojunction solar battery emitter stage, makes back contacts different
The efficiency of matter connection solar cell can obtain further lifting.
A kind of back contacts heterojunction solar battery emitter stage, from top to bottom including at least one layer of CrOxFilm.
Preferably, as the CrOxWhen film is more than two layers, CrO described in adjacent two layersxIt is additionally provided between film
Metallic film.
Preferably, when the back contacts heterojunction solar battery launches extremely one layer CrOxDuring film, the CrOx
The thickness of film is 5-20nm；Or when the emitter stage of the back contacts heterojunction solar battery includes two layers of CrOxDuring film,
CrO described in two layersxThe thickness of film is with being located at CrO described in two layersxThe thickness summation of metallic film between film is 5-20nm；
Or when the emitter stage of the back contacts heterojunction solar battery includes two layers of CrOxDuring film, CrO described in two layersxThe thickness of film
Degree is 5nm, located at CrO described in two layersxThe thickness of metallic film between film is 4nm.
Preferably, the metallic film be Au films, Ag films, Pd films, Cu films, Ni films, Mo films,
One kind in W film and Al films.
In order to solve identical technical problem, the present invention also provides a kind of back contacts heterojunction solar battery, including：Silicon substrate
Body, the first passivation layer located at the preceding surface of the silicon substrate, the second passivation layer of the back surface located at the silicon substrate, it is located at
The emitter stage as described above of the back surface of second passivation layer, the emitter electrode on the emitter stage and it is located at
Base electrode on second passivation layer.
Preferably, the back contacts heterojunction solar battery also includes being located at the base electrode and described second
Back surface field layer between passivation layer, or the back contacts heterojunction solar battery also include the preceding table located at first passivation layer
The antireflective coating in face.
Preferably, the back surface field layer is LiFxFilm, TiO2Film, MgFxFilm and Cs2CO3One in film
Kind.
Preferably, interdigitated configuration, and two phases are formed between the base electrode and the emitter electrode
Do not contacted between the adjacent base electrode and the emitter electrode.
In order to solve identical technical problem, the present invention also provides a kind of for preparing above-mentioned back contacts hetero-junctions sun electricity
The preparation method in pond, comprises the following steps：
Crystal silicon chip is chosen, the silicon substrate is formed after cleaning；
First passivation layer and second passivation layer are deposited respectively on the preceding surface and rear surface of the silicon substrate；
In the back surface stationary positioned template of second passivation layer, the first metal mask plate is embedded in the locating template
It is interior, it is sequentially depositing the CrO in the back surface of second passivation layerxFilm and/or metallic film, the emitter electrode；
First metal mask plate is removed, the second metal mask plate matched with first metal mask plate is embedding
Enter in the locating template, the back surface using evaporation in second passivation layer deposits the base electrode.
Preferably, it is included in the step of the back surface of second passivation layer deposits the base electrode described
The back surface of second passivation layer is sequentially depositing back surface field layer and the base electrode；Or deposit institute on the preceding surface of the silicon substrate
The preceding surface that first passivation layer is additionally included in after the step of stating the first passivation layer deposits the antireflective coating.
Compared with prior art, the beneficial effects of the present invention are：
(1) CrO is deposited by the back surface in the silicon substratexFilm is using the emitter stage as solar cell, the setting
On the one hand the emitter electrode on the emitter stage can be made not form light to the preceding surface of the silicon substrate to block, carried
The absorptivity of the high silicon substrate；On the other hand, using CrOxFilm is used as emitter stage, the CrOxFilm not only can be in institute
The contact area for stating the back surface of silicon substrate causes the movement of fermi level, is close to the conduction band of silicon, i.e. CrOxFilm can
Induce silicon face band curvature to produce space-charge region, it is obtained carrier selective exposure, it is ensured that the work of emitter stage
With；And use CrOxFilm also causes the emitter stage need not be doped in preparation process can be real as emitter stage
It is existing, from compound (i.e. the surface recombination and auger recombination) without emitter stage, in this way, also to use CrOxFilm conduct
The open-circuit voltage of the back contacts heterojunction solar battery of emitter stage is improved, so that the efficiency of overall lifting solar cell；
(2) CrO is usedxFilm or in adjacent two layers CrOxMetallic film is set up between film to be used as solar cell
Emitter stage, the solar cell of this structure there is no document and patent report, be a kind of silica-based solar cell of brand-new material；
(3) emitter stage of the invention is as a result of CrOxFilm, therefore, in its preparation process not only without doping but also can
Carried out with low temperature, in this way, can not only avoid inflammable easy caused by doped source in traditional solar cell emitter preparation process
The use of gas explosion body, improves security and the stability of solar cell, and can reduce production cost, is easy to HBC sun electricity
The large-scale production in pond；
(4) using the solar cell of the emitter stage in preparation process, transmitting polar body can be reduced by introducing oxygen bias
Area's defect state, improves transmitting polar body area and is combined；
(5) solar cell of the invention is by setting the first passivation layer and the on the preceding surface of the silicon substrate and back surface
Two passivation layers, can be passivated in the contact interface with silicon substrate, to reduce boundary defect state, improve back contacts hetero-junctions too
The open-circuit voltage in positive electricity pond, so as to further lift battery efficiency.
Brief description of the drawings
Fig. 1 is that the back contacts heterojunction solar battery emitter stage in the embodiment of the present invention is applied to the back contacts hetero-junctions sun
In the structural representation of battery, figure, extremely one layer CrO of transmitting of back contacts heterojunction solar batteryxFilm；
Fig. 2 is that the back contacts heterojunction solar battery emitter stage in the embodiment of the present invention is applied to the back contacts hetero-junctions sun
In the structural representation of battery, figure, the transmitting extremely trilamellar membrane structure of back contacts heterojunction solar battery is from top to bottom wrapped successively
Include CrOxFilm, Au films and CrOxFilm；
Fig. 3 is the schematic diagram of the back contacts heterojunction solar battery preparation method in the embodiment of the present invention, figure include a,
Five figures of b, c, d, e, each figure corresponds to the structure of the back contacts heterojunction solar battery under different step respectively；
Fig. 4 is the structural representation for positioning half tone in the embodiment of the present invention；
Fig. 5 is the structural representation of the first metal mask plate in the embodiment of the present invention；
Fig. 6 is the structural representation of the second metal mask plate in the embodiment of the present invention；
Fig. 7 is the flow chart of the back contacts heterojunction solar battery preparation method in the embodiment of the present invention；
Fig. 8 is the external quantum efficiency (EQE) of different back contacts heterojunction solar batteries in the embodiment of the present invention with wavelength
(Wavelength) change curve；
During Fig. 9 is the Suns-Voc test result figures of different back contacts heterojunction solar batteries in the embodiment of the present invention, figure
Effective sun number (Effective Suns) of different back contacts heterojunction solar batteries is reflected with open-circuit voltage (Voc) change
Change curve map；
Figure 10 is emitter stage respectively CrO in the embodiment of the present inventionxFilm and WoxThe back contacts hetero-junctions sun electricity of film
The efficiency (Efficiency) in pond with time (Days, i.e. number of days) change curve；
Wherein, 1, silicon substrate；2nd, the first passivation layer；3rd, the second passivation layer；4th, emitter stage；41st, CrOx films；42nd, metal
Film；5th, emitter electrode；6th, back surface field layer；7th, base electrode；8th, antireflective coating；9th, locating template；91st, the first metal mask
Plate；92nd, the second metal mask plate.
Embodiment
With reference to the accompanying drawings and examples, the embodiment to the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1：
As shown in figure 1, the back contacts heterojunction solar battery of the present invention, it includes silicon substrate 1, located at the silicon substrate 1
Preceding surface the first passivation layer 2, located at the silicon substrate 1 back surface the second passivation layer 3, located at second passivation layer
The emitter stage 4 of 3 back surface, the emitter electrode 5 on the emitter stage 4 and located at second passivation layer 3
On base electrode 7.
Wherein, the emitter stage 4 is the back contacts heterojunction solar battery emitter stage 4 of the present invention, in the present embodiment, should
Emitter stage 4 is the CrO for 5-20nm by a layer thicknessxFilm 41 is constituted, and the structure of certain emitter stage 4 is also not limited only to one
Layer CrOxThe structure of film 41.The back contacts heterojunction solar battery of the present invention is that the luminous energy of absorption is converted into electric energy, wherein,
The light absorbing layer of battery is mainly the silicon substrate 1, and the silicon substrate 1 absorbs the electron hole produced after photon and will distinguished
It is delivered to the base electrode 7 and the emitter electrode 5.
General, the base electrode 7 is provided in the back surface of the silicon substrate 1, and the emitter electrode 5 is to set
Put on the emitter stage 4, because the emitter stage 4 in the present embodiment is provided in the back surface of the silicon substrate 1, thus
Also so that the emitter electrode 5 also is located at the back surface of the silicon substrate 1, it is to avoid the preceding surface of the silicon substrate 1 is formed
Light is blocked, to improve the absorptivity of the silicon substrate 1, so as to improve battery efficiency.At the same time, due in the present embodiment
The emitter stage 4 is the CrO used againxFilm 41, and CrOxThe material that film 41 is used is high work function material, and the material can
Cause the movement of fermi level with the contact area in the back surface of the silicon substrate 1, be close to the conduction band of silicon, i.e. CrOxIt is thin
Film 41 can induce silicon face band curvature to produce space-charge region, it is obtained carrier selective exposure, play hair
The effect (i.e. the transmission and collection of carrier) of emitter-base bandgap grading 4；Moreover, using CrOxFilm 41 also causes the transmitting as emitter stage 4
Pole 4 need not be doped in preparation process can be achieved, from without emitter stage 4 it is compound (i.e. surface recombination with
Auger recombination), in this way, also make it that the open-circuit voltage of the back contacts heterojunction solar battery using the emitter stage 4 is improved, from
And the overall efficiency for lifting battery.
Further, since emitter stage 4 need not adulterate in preparation process, thus traditional solar cell can be not only avoided to launch
In the preparation process of pole 4 caused by doped source flammable explosive gas use, improve security, and can reduce and be produced into
This, is easy to the large-scale production of HBC solar cells.
In order to reduce the silicon substrate 1 a front surface and a rear surface it is compound, also in the silicon substrate 1 in the present embodiment
Preceding surface is provided with first passivation layer 2, is provided with described between the back surface and the emitter stage 4 of the silicon substrate 1
Second passivation layer 3, first passivation layer 2 and second passivation layer 3 are SiOxFilm, naturally it is also possible to use TiO2、
Al2O3Passivation layer is used as Deng film.Specifically, the SiOxFilm can be passivated in the contact interface with silicon substrate 1, with
Boundary defect state is reduced, to improve the open-circuit voltage of back contacts heterojunction solar battery, so as to further lift battery efficiency.
In addition, being also provided with back surface field layer 6 between second passivation layer 3 and the base electrode 7 in the present embodiment.Tool
Body, the back surface field layer 6 is LiFxFilm, naturally it is also possible to be TiO2Film, MgFxFilm and Cs2CO3The low work functions such as film
The film that material makes.Due to LiFxThe material that film is used is low-work-function material, therefore, and with high work function material
Above-mentioned emitter stage 4 together, can promote the movement of the fermi level of the surface area contact of silicon substrate 1 well, promote carrier
To separation, selectively transmitted with obtaining more preferable carrier, so as to further lift battery efficiency.
It is understood that in order to absorb light as far as possible, further improving battery efficiency, sunken light knot can also be set up
Structure.Specifically, being also provided with one on the preceding surface of first passivation layer 2 of back contacts heterojunction solar battery in the present embodiment
Layer antireflective coating 8, the antireflective coating 8 is that light knot is fallen into formed by pyramid matte by being prepared on the surface of the silicon substrate 1
Structure, can further improve the absorptivity of battery, so as to improve battery efficiency
In order to obtain in above-mentioned back contacts heterojunction solar battery, the present embodiment using step progress as shown in Figure 7
Prepare：
Step S100：Crystal silicon chip is chosen, the silicon substrate is formed after cleaning.
Specifically, choosing n-type monocrystalline silicon piece, silicon chip is cleaned using RCA cleanings, by the cutting on silicon chip
Vestige and impurity etc. are removed so that silicon substrate 1 (as shown in the figure a in Fig. 3) in subsequent technique can have it is higher pure
Cleanliness, it is to avoid the efficiency of influence integral battery door.
Wherein, main in RCA cleanings is H by proportioning2SO4：H2O2=3：1 SPM solution is to remove on silicon chip
Organic matter, by proportioning be HF：H2O=1：30 DHF solution is to remove the oxide layer on silicon chip, by matching as NH4OH：
H2O2：H2O=1：1：5 APM solution is to remove the granule foreign on silicon chip, by matching as HCl：H2O2：H2O=1：1：6
HPM solution is to remove the metal impurities on silicon chip.
Step S200：As shown in the figure b in Fig. 3, using plasma enhancing chemical vapour deposition technique (Plasma
Enhanced Chemical Vapor Deposition, abbreviation PECVD) on the preceding surface and rear surface of the silicon substrate 1 point
First passivation layer 2 and second passivation layer 3, i.e. SiN are not depositedxFilm.Wherein, deposition power is 2400W, deposition gas
Press as 20Pa, the gas flow ratio of ammonia and silane is 2:1, depositing temperature is 450 DEG C, the SiN being depositedxThe thickness of film
For 75nm.In addition it is also possible to the depositing antireflection film 8 as needed on second passivation layer 3 (as shown in the c in Fig. 3).
Step S300：As shown in the figure d in Fig. 3, (such as scheme in the back surface stationary positioned template 9 of second passivation layer 3
Shown in 4), the inframe that the embedded locating template 9 (as shown in Figure 5) of the first metal mask plate 91 is formed, using evaporation
(the CrO of emitter stage 4 is sequentially depositing in the back surface of second passivation layer 3 by resistance-type thermal evaporation coating machinexFilm
41) with the emitter electrode 5 (Al films).
First metal mask plate 91 is supporting with the locating template 9, wherein the locating template 9 is framework knot
Structure, shape of its shape typically with the silicon substrate 1 is corresponding, can form spacing well to first metal mask plate 91
Effect, it is to avoid first mask plate is moved in preparation process.And first mask plate is comb form, when by institute
When stating the first mask plate and covering on the back surface of second passivation layer 3, first mask plate can be carried out to its subregion
Block, and the CrOxWhat the back surface that film 41 is deposited upon second passivation layer 3 was not covered by first mask plate
Region, so as to also cause the CrOxEmitter stage 4 and be deposited on the CrO that film 41 is formedxEmitter electrode on film 41
5 be also comb form.
In above-mentioned deposition process, it is about 5 × 10 that need to control vacuum-4Pa, and oxygen is passed through, and oxygen bias is 3 × 10-2Pa, plated film speed isIn this way, the CrO of depositionxThe thickness of film 41 can be controlled in 5-20nm, and emitter electrode 5
Thickness be 1 μm, in this way, can both ensure that the emitter stage 4 was sufficiently contacted with the emitter electrode 5, can ensure again
Ohmic loss on the emitter electrode 5 is relatively low.Because the deposition process is carried out at normal temperatures, therefore, not only equipment
Simply, cost is low, and can avoid the phase counterdiffusion of the storeroom caused by high temperature, it is ensured that battery efficiency.Further, since heavy
During product, oxygen bias is also introduced, and hence it is also possible to reduce the body area defect state of emitter stage 4, improves the body area of emitter stage 4 and is combined.
The CrO can certainly be deposited using other methodsxFilm 41.
Step S400：As shown in the figure e in Fig. 3, after the emitter stage 4 and the emitter electrode 5 are prepared, remove
First metal mask plate 91, by the second metal mask plate 92 matched with first metal mask plate 91 (such as Fig. 6 institutes
Show) in the embedded locating template 9, still using evaporation by resistance-type thermal evaporation coating machine in second passivation layer 3
Back surface deposit the base electrode 7.
Certainly, in order to improve battery efficiency, can also using evaporation by resistance-type thermal evaporation coating machine described the
The back surface of two passivation layers 3 first deposits the (LiF of back surface field layer 6xFilm), deposit the base in the back surface field layer 6 afterwards
Electrode 7 (Al films), and in the present embodiment, the thickness of back surface field layer 6 is 1.5nm, the base electrode 7 is 1 μm.
During this, because the second metal mask plate 92 of use is and the shape phase of the first metal mask plate 91
Match somebody with somebody, be also comb form, in this way, in deposition, by the way that second metal mask plate 92 is fixed in the locating template 9
Afterwards, second metal mask plate 92 can cover the emitter stage 4 and the emitter electrode 5 well, so that after avoiding
The continuous back surface field layer 6 formed is connected with the emitter stage 4, the emitter electrode 5 respectively with the base electrode 7.And compared with
Good, the mask plate used in the present embodiment can to form interdigital between the base electrode 7 and the emitter electrode 5
Do not contacted between shape structure, and two adjacent base electrodes 7 and the emitter electrode 5.Specifically, in the present embodiment
In the distance between two adjacent base electrodes 7 and the emitter electrode 5 be 75 μm, this certain spacing is smaller more
It is good.
Embodiment 2：
As shown in Fig. 2 the present embodiment is in back contacts heterojunction solar battery in the present embodiment with the difference of embodiment 1
Emitter stage 4 be trilamellar membrane structure, its from top to bottom be respectively one layer of CrOxFilm 41, layer of metal film 42, one layer of CrOxIt is thin
Film 41, wherein CrOxThe thickness of film 41 is 5nm, and the thickness of metallic film 42 is 4nm.Metallic film 42 in the present embodiment
For Au films, naturally it is also possible to be the metallic film 42 of other high work(work function materials, for example Ag films, Pd films, Cu films,
Ni films, Mo films, W film and Al films etc..It is understood that back contacts heterojunction solar battery emitter stage 4 may be used also
To be by multi-layer C rOxFilm 41 is constituted, and adjacent two layers CrOxMetallic film 42 is provided between film 41, and is not limited only to this
Structure in embodiment.
Accordingly, the back contacts heterojunction solar battery in the present embodiment is in preparation process, with not existing together for embodiment 1
It is, in the present embodiment when depositing the emitter stage 4, the technique in embodiment 1 need to be used to be sequentially depositing 5nm CrOxFilm
41st, 4nm Au films and 5nm CrOxFilm 41.Certainly, the CrO can also be deposited using other method in the present embodimentx
Film 41 and the metallic film 42.
The emitter stage 4 of back contacts heterojunction solar battery in the present embodiment is as a result of metal-oxide film/gold
Belong to the structure of the metal-oxide film of film 42/ (OMO), therefore, the emitter stage 4 is exempted from doping and low temperature system
It is standby, but also the carrier concentration of metal oxide can be improved, to form the low body area of emitter stage 4, Interface composites and low contact
The induction type p-n junction of resistance, so as to improve battery efficiency.
Embodiment 3：
The present embodiment is using the CrO with different-thickness prepared by the preparation method of embodiment 1xFilm 41, difference
Back surface field layer (the LiF of thicknessxFilm) back contacts heterojunction solar battery (cell area is 4cm2), the preceding table of the solar cell
Face employs SiNx/SiOx lamination reduced passivation resisting films, and the device parameter performance of the solar cell is to test to obtain under the conditions of STC
), the device parameter performance of the solar cell is as shown in Table 1：
Table one
It can be found that transmitting extremely 5nm CrO from table onexBack contacts heterojunction solar battery, its opto-electronic conversion effect
Rate reaches that maximum is 13.55%, compared to transmitting extremely 10nm, 15nm and 20nm CrOxThe back contacts hetero-junctions sun electricity
Pond, its fill factor, curve factor is up to 59.80%.
Shown in table one, with CrOxThe increase of film thickness, can cause solar cell series connection resistance increase, so as to cause
Fill factor, curve factor is reduced, and thus illustrates CrOxFilm body resistivity is larger.And launch extremely 5nm CrOxThe back contacts hetero-junctions sun
The open-circuit voltage reduction of battery, is, because film is also in discontinuous state, complete covering to be unable to reach in silicon chip surface,
With higher recombination current density.And launch extremely 10nm CrOxFilm in deposition process due to that can reach liaison shape
State, therefore preferable inactivating performance can be formed to emitter region, reach the open-circuit voltage of the solar cell corresponding to it
600mV。
It is respectively 2nm LiF by comparing back surface field layerxFilm and 1nmLiFxThe back contacts heterojunction solar battery of film, can
To find with LiFxThe reduction of film thickness, the open-circuit voltage and fill factor, curve factor of corresponding solar cell have declined, therefore
The setting of back surface field layer can reduce surface recombination.Specifically, as shown in figure 8, curve shown in Fig. 8 is to introduce 2 in corresponding table one
×10-2The external quantum efficiency (abbreviation EQE) of the different back contacts heterojunction solar batteries of Pa oxygen bias.From the figure, it can be seen that
Using 2nm LiFxAs the back contacts heterojunction solar battery of back surface field layer, and EQE is in wavelength (Wavelength) scope
400nm-850nm, has been up to more than 90%, illustrates that emitter stage exists with back surface field layer less compound.And use 1nm
LiFxIt can be reduced as the EQE of the back contacts heterojunction solar battery of back surface field layer.It is primarily due to back contact battery and there is electricity
Block, 1nm LiFxBack surface field layer there is larger compound, process of the minority carrier in Gui Ti areas lateral transport to emitter stage
It is middle to be combined, cause short-circuit current density to reduce 2mA/cm2。
By comparing transmitting extremely 5nm CrOxThere is no the back contacts hetero-junctions for introducing oxygen bias in film and preparation process
Solar cell and transmitting extremely 5nm CrOxThe back contacts heterojunction solar battery that oxygen bias is introduced in film and preparation process can
To find, launch extremely 5nm CrOxThere is no the back contacts heterojunction solar battery for introducing oxygen bias in film and preparation process
Open-circuit voltage reduces 65mV, and its fill factor, curve factor reduces 2.8%.And this is primarily due to CrO3Produced in thermal evaporation process
Raw substantial amounts of oxygen vacancy, causes CrOx/ n-Si band curvatures amount is reduced, and can reduce fill factor, curve factor and open-circuit voltage.Therefore, introduce
Oxygen bias can reduce CrOxThe formation of oxygen vacancy in film, improves the performance of battery.
Further, as shown in figure 9, Fig. 9 is the Suns-V of the different back contacts heterojunction solar batteries corresponding to table oneOC
Test result curve map, as it can be seen in figure 9 that the CrO of different-thicknessxBack contacts heterojunction solar battery corresponding to film
Open-circuit voltage under high light injection does not occur in the phenomenon reversely deflected, therefore above-mentioned each back contacts heterojunction solar battery
In the absence of schottky junction, effective induction type p-n junction is formd.Meanwhile, this result also indicates that emitter stage uses CrOxDuring film
Prepared back contacts heterojunction solar battery has efficient potentiality.
Embodiment 4：
To extremely one layer 5nm CrO of transmitting in the present embodimentxFilm, one layer of 10nm CrOxFilm and two layers of 5nm CrOxIt is thin
The performance parameter of the back contacts heterojunction solar battery of film (centre is 4nm Au films) compares, referring specifically to table two.Its
In, launch extremely 5nm CrOxExtremely one layer 10nm CrO of film or transmittingxThe back contacts heterojunction solar battery of film is used
Preparation method in embodiment 1, and launch extremely two layers 5nm CrOxThe back contacts heterojunction solar battery of film is using implementation
The preparation method of example 2, and three battery steps corresponding in preparation process are all consistent.
Table two
It can be found that extremely two layers 5nm CrO of transmitting from table twoxThe back contacts heterojunction solar battery of film compared to
Other two back contacts heterojunction solar batteries, its battery efficiency improves 1.88% and 3.47% respectively.And 4nm Au is thin
Film is inserted into 10nm CrOxThe open-circuit voltage and fill factor, curve factor of solar cell are significantly improved in film, and this is primarily due to
4nm Au improve CrOxThe concentration of carrier in film, reduces 10nm CrOxThe bulk resistor of film.
It is respectively 5nm CrO that Figure 10, which compares emitter stage,xFilm and 10nm WOxThe back contacts heterojunction solar battery of film
Stability, from the curve in figure can be seen that transmitting extremely 10nm WOxThe back contacts heterojunction solar battery of film occurs
The extension continuous decrease of continuation decay, i.e. battery efficiency over time, and this moisture, carbon being primarily due in air is miscellaneous
Matter etc. influences.And launch extremely 5nm CrOxThe back contacts heterojunction solar battery of film was decayed in first 10 days, then
Efficiency brings up to 15% again.Therefore, emitter stage uses CrOxFilm can make its corresponding back contacts heterojunction solar battery tool
There is higher stability.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvement and replacement can also be made, these improve and replaced
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of emitter stage of back contacts heterojunction solar battery, it is characterised in that from top to bottom including at least one layer of CrOxIt is thin
Film.
2. the emitter stage of back contacts heterojunction solar battery as claimed in claim 1, it is characterised in that as the CrOxFilm
For more than two layers when, CrO described in adjacent two layersxMetallic film is additionally provided between film.
3. the emitter stage of back contacts heterojunction solar battery as claimed in claim 2, it is characterised in that when the back contacts are different
Matter connection solar cell launches extremely one layer CrOxDuring film, the CrOxThe thickness of film is 5-20nm；Or when the back contacts
The emitter stage of heterojunction solar battery includes two layers of CrOxDuring film, CrO described in two layersxThe thickness of film is with being located at described in two layers
CrOxThe thickness summation of metallic film between film is 5-20nm；Or when the transmitting of the back contacts heterojunction solar battery
Pole includes two layers of CrOxDuring film, CrO described in two layersxThe thickness of film is 5nm, located at CrO described in two layersxBetween film
The thickness of metallic film is 4nm.
4. the emitter stage of back contacts heterojunction solar battery as claimed in claim 2 or claim 3, it is characterised in that the metal foil
Film is one kind in Au films, Ag films, Pd films, Cu films, Ni films, Mo films, W film and Al films.
5. a kind of back contacts heterojunction solar battery, it is characterised in that including：Silicon substrate, the preceding surface located at the silicon substrate
The first passivation layer, located at the silicon substrate back surface the second passivation layer, the back surface located at second passivation layer
Emitter stage as described in any one of 1-4, the emitter electrode on the emitter stage and on second passivation layer
Base electrode.
6. back contacts heterojunction solar battery as claimed in claim 5, it is characterised in that the back contacts hetero-junctions sun electricity
Pond is also included located at the back surface field layer between the base electrode and second passivation layer, or the back contacts hetero-junctions sun
Battery also includes the antireflective coating located at the preceding surface of first passivation layer.
7. back contacts heterojunction solar battery as claimed in claim 6, it is characterised in that the back surface field layer is LiFxFilm,
TiO2Film, MgFxFilm and Cs2CO3One kind in film.
8. back contacts heterojunction solar battery as claimed in claim 5, it is characterised in that the base electrode and the transmitting
Formed and do not contacted between interdigitated configuration, and two adjacent base electrodes and the emitter electrode between the electrode of pole.
9. a kind of preparation method of back contacts heterojunction solar battery, connects for preparing the back of the body described in claim any one of 5-8
Touch heterojunction solar battery, it is characterised in that comprise the following steps：
Crystal silicon chip is chosen, the silicon substrate is formed after cleaning；
First passivation layer and second passivation layer are deposited respectively on the preceding surface and rear surface of the silicon substrate；
In the back surface stationary positioned template of second passivation layer, the first metal mask plate is embedded in the locating template,
The CrOx films and/or metallic film, the emitter electrode are sequentially depositing in the back surface of second passivation layer；
First metal mask plate is removed, institute will be embedded in the second metal mask plate that first metal mask plate matches
State in locating template, the back surface using evaporation in second passivation layer deposits the base electrode.
10. the preparation method of back contacts heterojunction solar battery as claimed in claim 9, it is characterised in that
The step of back surface in second passivation layer deposits the base electrode is included in second passivation layer
Back surface is sequentially depositing back surface field layer and the base electrode；
Or first passivation is additionally included in after the step of preceding surface of the silicon substrate deposits first passivation layer
The preceding surface of layer deposits the antireflective coating.
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