CN114937706B - Laminated passivation film for crystalline silicon solar cell and preparation method thereof - Google Patents
Laminated passivation film for crystalline silicon solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
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- 238000000151 deposition Methods 0.000 claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010703 silicon Substances 0.000 claims abstract description 38
- 230000008021 deposition Effects 0.000 claims abstract description 31
- 229910052796 boron Inorganic materials 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 boron ions Chemical class 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 13
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 20
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 19
- 229920005591 polysilicon Polymers 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 238000007650 screen-printing Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 5
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 4
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- 238000000137 annealing Methods 0.000 description 9
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
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- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01L31/04—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 at least one potential-jump barrier or surface barrier
- H01L31/068—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction 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
- H01L31/18—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a laminated passivation film for a crystalline silicon solar cell and a preparation method thereof. The laminated passivation film of the invention is composed of B 2 O 3 The laser-doped p-type local doping device comprises a layer, a passivation film cover layer and a hydrogen-containing cover layer, and p-type local doping is realized by utilizing a laser technology. Deposition of B by atomic layer deposition techniques 2 O 3 A layer serving as a passivation layer and a doping source layer, B 2 O 3 The layers are uniformly distributed and thus the B is utilized subsequently 2 O 3 When the layer is doped by laser irradiation, boron ions are uniformly distributed in the diffusion region; the method directly carries out boron p on the silicon substrate by laser irradiation + Doping and windowing are realized at the same time, and damage to the silicon substrate can be greatly reduced by reasonably regulating and controlling laser parameters. The preparation method of the invention basically uses the current mainstream mode, so that the compatibility of the method and the existing production line is higher, and the preparation method can be realized without specially designing a new process and a new production line, thereby greatly reducing the production cost of the new method popularization.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a laminated passivation film for a crystalline silicon solar cell and a preparation method thereof.
Background
With the progress of the current silicon production and purification technology, the carrier recombination problem caused by the existence of internal defects or impurities of silicon has little influence, and the important factor which restricts the energy conversion efficiency of the crystalline silicon solar cell is the carrier recombination problem on the surface of silicon.
Passivation emitter and back contact (PERC) cells currently mainstream in the industry achieve carrier separation and collection by doping p-n, front and back ends respectively by SiN x And Al 2 O 3 /SiN x The laminated passivation film reduces the carrier recombination rate and improves the energy conversion efficiency. Similarly, with the generation of new passivation film technology, amorphous silicon heterojunction cells and tunneling silicon oxide passivation contact cells are expected to become the mainstream high-efficiency crystalline silicon cells in the future. The heterojunction battery uses intrinsic hydrogenated amorphous silicon as a passivation film, but the passivation film has larger optical parasitic absorption, and the passivation effect is sensitive to high temperature; tunneling silicon oxide passivation contact cells use a silicon oxide/heavily doped polysilicon stack to reduce the recombination rate of surface carriers, but polysilicon filmsThere are still some problems with the deposition, doping process. The trend in the future photovoltaic industry is to use larger area, thinner silicon wafers, and the effect of the surface carrier recombination problem on the conversion efficiency of the battery device is more remarkable for the thin silicon wafers. International photovoltaic technology route 2021 indicates that PERX series cells, tunnel silicon oxide passivation contact cells, amorphous silicon heterojunction cells, such as PERC and passivated emitter back partial diffusion (PERL) will gradually occupy market bodies for five to ten years in the future. In this context, there is still a need for efficient passivation films in the future to further improve battery efficiency.
At present, the mainstream crystalline silicon battery in the market still mainly comprises a doped p-n junction, and a passivation film material is required to have a good passivation effect on a p-type or n-type region on the surface, so that the photon-generated carrier recombination is reduced, and the battery efficiency is improved. The p-type/n-type emitters of a typical cell are respectively through BBr 3 /POCl 3 The high-temperature thermal diffusion is obtained, and in addition, the p-type/n-type doping can be realized by ion implantation and in-situ oxidation annealing modes.
The silicon dioxide by the thermal oxidation method has passivation effect on the surfaces of p-type and n-type silicon formed by boron and phosphorus diffusion, and the passivation effect on an n-type emitter is superior to that of the p-type silicon; subsequent plasma chemical vapor deposition (plasmachemical vapor deposition, PECVD) of SiN x Provides a low-temperature passivation process at 300-400 ℃, which is suitable for passivating an n-type emitter and has good surface passivation performance (dark saturation current density J) 0 ＝30～40fA/cm 2 ) The passivation effect mainly derives from a field passivation mechanism; siO by thermal oxidation 2 /PECVD SiN x The lamination can better passivate n + Emitter (dark saturation current density J) 0 ＝12～25fA/cm 2 ) In addition, siO by thermal oxidation 2 A thin aluminum cover layer, namely aluminum annealed silicon oxide, is added in the annealing process at 400 ℃ to achieve the purpose of SiO by a thermal oxidation method 2 /PECVD SiN x The passivation effect is as excellent as the lamination. B.Hoex et Al utilize PECVD Al 2 O 3 Achieves good passivation of p-type emitter (J) 0 ＝10fA/cm 2 ) The Al is 2 O 3 Field passivation caused by negative charges in the film is a main passivation mechanism; engelhardt et al human hairAt present PECVD SiO x :B/SiN y The stack also has good passivation effect on p-type emitter (J 0 ＝40fA/cm 2 ) Wherein SiO is x B can be used as the forming of p + The doped source layer of the emitter can also be used as a passivation layer.
The efficiency of p-type PERC cells that have been mass produced is still currently limited by high carrier recombination losses at the crystalline silicon-electrode contact interface, as well as auger recombination, band gap narrowing and free carrier absorption problems caused by heavy doping. The back of the p-type PERC battery on the production line passes through Al 2 O 3 /SiN x Passivation is carried out on the lamination, laser grooving is combined, and high-temperature sintering of screen printing aluminum paste is carried out to realize p + A local back field. Research shows that to inhibit carrier recombination at the contact of the back electrode and reduce contact resistance, on the one hand, local Al doping with considerable depth is required + The back field, on the other hand the Al doping concentration of this region should be sufficiently high. Accordingly, the process has the following problems: 1) To increase the solid solubility of Al in Si, i.e. the doping concentration, the temperature of the sintering process needs to be increased, thus creating a sintering temperature adaptation problem for the back side aluminum paste and front side silver paste, resulting in Al doping p + The carrier recombination current density of the local back surface field is larger and is opposite to the back surface Al 2 O 3 /SiN x The passivation effect of the film causes damage; 2) Due to the difference of diffusion coefficients of Al and Si, kerr holes exist, and the existence of the holes leads to the doping of Al with p + The formation of local back field is blocked, so that the contact resistance becomes large; 3) The spacing of the laser-driven point contacts and the thickness and height of the printed aluminum paste affect the final Al-doped p + Is difficult to control.
Research shows that the solid solubility of boron in silicon is higher, so that the doping concentration can be higher by an order of magnitude, thereby being beneficial to reducing the contact resistance and the gain passivation effect; and the presence of B is beneficial to reducing the presence of k-holes and increasing the back field thickness. The current boron local doping mode mainly comprises the following steps: and (3) boron ion implantation, sintering boron-containing aluminum slurry, and carrying out wire mesh brushing on the boron-containing silicon slurry and laser irradiation. The boron ion implantation mode damages silicon, causes various defects to aggravate carrier recombination, and the method has high cost and is difficult to realize local doping. The way in which the boron-containing aluminum slurry is sintered mainly has the following problems: (1) boron maldistribution; (2) The sintering time is short, only a few seconds, while boron diffusion into the Al-Si liquid takes time. The screen brushing of the boron-containing silicon slurry and the laser irradiation mode require removal of useless slurry which is not irradiated by laser, and the process difficulty and the cost are increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a laminated passivation film for a crystalline silicon solar cell and a preparation method thereof.
The preparation method of the laminated passivation film for the crystalline silicon solar cell comprises the following steps:
(1) Depositing B on the surface of a cleaned crystalline silicon substrate 2 O 3 Layer B of 2 O 3 The layer is prepared by ALD;
(3) At said B 2 O 3 Sequentially depositing a passivation film cover layer and a hydrogen-containing cover layer on the layer to form a laminated passivation film;
(3) Slotting on the laminated passivation film by picosecond laser technology to form molten state on at least part of silicon surface at slotting position, and to enable the B to be formed 2 O 3 The layer diffuses into the partially melted silicon surface as a boron dopant source, forming a p-type heavy doping.
As a further improvement of the invention, the B 2 O 3 The deposition thickness of the layer is 1-50 nm.
As a further improvement of the invention, the passivation film cover layer comprises Al 2 O 3 、TiO 2 、Ga 2 O 3 、Ta 2 O 5 One or more of the passivation film cover layers are deposited by ALD or PECVD, and the deposition thickness is 5-100 nm.
As a further improvement of the present invention, the hydrogen-containing cap layer comprises SiN x 、SiO x 、SiC x One or more of the hydrogen-containing cover layers is deposited by PECVD, and the deposition thickness is 10-200 nm.
The laminated passivation film for the crystalline silicon solar cell is prepared by the preparation method of the laminated passivation film for the crystalline silicon solar cellThe preparation method comprises the following steps of sequentially depositing: the B is 2 O 3 A layer; the passivation film cover layer; the hydrogen-containing cap layer; and p-type local doping is realized by utilizing a laser technology.
As a further improvement of the invention, the passivation film cover layer is Al 2 O 3 The hydrogen-containing cover layer is SiN x 。
The preparation method of the crystalline silicon solar cell uses the laminated passivation film for the crystalline silicon solar cell.
As a further improvement of the invention, the preparation method of the crystalline silicon solar cell as a PERC cell comprises the following steps:
(1) Selecting a p-type silicon substrate and texturing;
(2) Preparing an n-type doped emitter and a corresponding passivation film of a p-type PERC-based battery on the front surface of the battery;
(3) Preparing a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 on the back surface of the cell;
(4) Preparing a metal silver electrode on the front side of the battery, preparing a metal aluminum electrode on the back side of the battery, performing high-temperature sintering, and burning through SiN with front silver paste x And n + Ohmic contacts are formed for electron collection and back aluminum electrodes are used for collecting holes.
As a further improvement of the present invention, the preparation method of the crystalline silicon solar cell being a TOPCon-BJ cell comprises the steps of:
(1) Selecting a p-type silicon substrate and texturing;
(2) Preparation of ultra-thin SiO based TOPCON cells on the cell backside 2 Superposing an electron selective transmission layer of n-type heavily doped polysilicon and a corresponding passivation film;
(3) Preparing a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 on the front surface of the cell;
(4) Preparing a metal aluminum electrode on the front side of the battery, preparing a silver aluminum composite electrode on the back side of the battery, performing high-temperature sintering, and burning through SiN by using silver aluminum composite slurry on the back side x And n + Ohmic contacts are formed for electron collection.
As a further improvement of the invention, the preparation method of the crystalline silicon solar cell which is a TOPCon-IBC cell comprises the following steps:
(1) Selecting a p-type polished silicon substrate;
(2) Preparation of ultra-thin SiO based TOPCON cells on the cell backside 2 Superposing an electron selective transmission layer of n-type heavily doped polysilicon;
(3) Preparing a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 on the front surface and the back surface of the cell;
(4) Manufacturing a separation electrode, screen printing an aluminum electrode in a p-type region, screen printing a silver-aluminum composite electrode in an n-type emitter region, and regulating and controlling a proper temperature to perform high-temperature sintering;
(5) And removing the back field region and the emitter region contact electrode by using a specific process to form the interdigital positive and negative electrodes. The invention has the beneficial effects that:
1. deposition of a layer B by Atomic Layer Deposition (ALD) techniques 2 O 3 This layer B 2 O 3 The silicon nitride can be used as a passivation layer and a doping source of a subsequent boron doping process, and the purpose of one-step and multi-use is realized.
2. The boron source used in the invention is deposited on the surface of the silicon substrate by ALD technology, and the distribution of the boron source is more uniform compared with other processes, thus the boron source is used later 2 O 3 When the laser irradiation doping is carried out, the uniformity of boron ions distributed in the diffusion region is far higher than that of the prior related local doping process.
3. When the method is used for carrying out boron doping on the silicon substrate, the method can avoid the mode of using ion implantation in the prior art because of directly opening a window by laser irradiation, thereby reducing the requirement on doping equipment and avoiding the problem of high loss on the equipment caused by using a boron source as the ion implantation.
4. The preparation method of the invention basically uses the current mainstream mode, so that the compatibility of the method and the existing production line is higher, and the preparation method can be realized without specially designing a new process and a new production line, thereby greatly reducing the production cost of the new method popularization.
5. When the p+ region is formed by utilizing laser irradiation, the invention adopts the inherent step of windowing by using the laser irradiation in the prior art, thereby saving the process flow and improving the production efficiency.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention, as well as the preferred embodiments thereof, together with the following detailed description of the invention, given by way of illustration only, together with the accompanying drawings.
Drawings
FIG. 1A is a schematic illustration of preparation B described in example 1 2 O 3 /Al 2 O 3 /SiN x Laminated passivation film and formation of local p + A process flow diagram of the front/back field.
FIG. 1B is a B prepared by the process described in example 1 2 O 3 /Al 2 O 3 /SiN x Laminated passivation film and formation of local p + Schematic of the front/back field.
Fig. 2A is a process flow diagram of the crystalline silicon solar cell structure of embodiment 2.
Fig. 2B is a schematic view of the crystalline silicon solar cell structure described in embodiment 2.
Fig. 3A is a process flow diagram of the crystalline silicon solar cell structure of embodiment 3.
Fig. 3B is a schematic structural diagram of the crystalline silicon solar cell described in embodiment 3.
Fig. 4A is a process flow diagram of the crystalline silicon solar cell structure of example 4. Fig. 4B is a schematic structural diagram of the crystalline silicon solar cell described in embodiment 4.
Marking:
101. silicon substrate
102、B 2 O 3 Layer(s)
103、Al 2 O 3 Layer(s)
104、SiN x Layer(s)
105. Front field/back field
201. Silicon substrate
202. n-type emitter
203、B 2 O 3 Layer(s)
204、Al 2 O 3 Layer(s)
205. Front SiN x Layer(s)
206. Backside SiN x Layer(s)
207、p + Local back field
208. Metal aluminum electrode
209. Metallic silver electrode
301. Silicon substrate
302、SiO 2 Layer(s)
303. Phosphorus doped polysilicon
304、B 2 O 3 Layer(s)
305. Front Al 2 O 3 Layer(s)
306. Reverse Al 2 O 3 Layer(s)
307. Front SiN x Layer(s)
308. Reverse SiN x Layer(s)
309、p + Local front field
310. Metal aluminum electrode
311. Metal silver aluminium composite electrode
401. Silicon substrate
402、SiO 2 Layer(s)
403. Phosphorus doped polysilicon layer
404、B 2 O 3 Layer(s)
405、Al 2 O 3 Layer(s)
406、SiN x Layer(s)
407、p + Local back field
408. Aluminum electrode
409. Silver-aluminum composite electrode
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention provides a laminated passivation film structure for a crystalline silicon solar cell, which comprises the following components:
(1)B 2 O 3 layer B of 2 O 3 The thickness of the layer is 1-50 nm, and the layer is used as a passivation and p-type doping source layer to be contacted with a silicon substrate;
(2) A passivation film cover layer, which is connected with the B 2 O 3 A passivation film cover layer having a thickness of 5-100 nm and comprising Al 2 O 3 、TiO 2 、Ga 2 O 3 、Ta 2 O 5 One or more of them.
(3) A hydrogen-containing cap layer in contact with the passivation film cap layer, the hydrogen-containing cap layer having a thickness of 10 to 200nm, the hydrogen-containing cap layer comprising SiN x 、SiO x 、SiC x One of or SiO x 、SiC x With SiN x Is a combination of (a) and (b).
The preparation method of the laminated passivation film for the crystalline silicon solar cell comprises the following steps:
(1) Deposit B on the surface of a cleaned silicon substrate 2 O 3 A layer serving as a passivation layer and a p-type doping source layer, B 2 O 3 The layer is prepared by ALD, and the thickness is 1-50 nm;
(2) At B 2 O 3 Depositing a passivation film cover layer comprising Al on the layer 2 O 3 、TiO 2 、Ga 2 O 3 、Ta 2 O 5 One or more of the above is/are deposited by ALD or PECVD, and the thickness is 5-100 nm;
(3) Depositing a hydrogen-containing cap layer comprising SiN over the passivation film cap layer x 、SiO x 、SiC x One or more of the materials adopts PECVD deposition technology, and the thickness is 10-200 nm;
(4) Annealing in nitrogen-hydrogen mixed gas at 300-600 deg.c for 5-60 min;
(5) Slotting by picosecond laser technology, B under the action of laser beam 2 O 3 The layer is used as a B doping source to be diffused to the surface of the local molten Si, so that local p-type doping is realized.
Passivation mechanism of the laminated passivation film: the laminated passivation film has high-density fixed charges and can play a role of field passivation. The outer hydrogen-containing cover layer is SiN deposited by PECVD technique x 、SiC x 、SiO x Etc. by diffusion of H into Si-B 2 O 3 The interface, saturated surface dangling bond realizes chemical passivation. In summary, the passivation stack combines two mechanisms of field passivation and chemical passivation to achieve efficient passivation. The hydrogen-containing cap layer can also act as an anti-reflective film to further reduce parasitic absorption and reflectivity if at the front end of the stack.
The invention also provides a solar cell with the laminated passivation film structure for the crystalline silicon cell. On one hand, the good passivation of the silicon surface is realized, and on the other hand, the co-doping of p with boron and aluminum can be realized by combining laser and aluminum paste sintering + A local back field. Based on this, the crystalline silicon cell structure presented by the present invention can be divided into two categories: the first category applies the laminated passivation film structure to the front surface of the crystalline silicon cell, passivates the front surface and forms a front field; the second type applies the laminated passivation film structure to the back surface of the crystalline silicon cell, passivating the back surface and forming a back field.
Example 1
The laminated passivation film structure for the crystalline silicon solar cell provided by the embodiment comprises B which are sequentially arranged 2 O 3 Layer of Al 2 O 3 Layer of SiN x And the layer is formed, and p-type local doping is realized by utilizing a laser technology.
The process flow chart and structure of the preparation process of the laminated passivation film for the crystalline silicon solar cell are shown in fig. 1A and 1B, and mainly comprise the following steps:
(1) Selecting a p-type monocrystalline silicon wafer, polishing, etching and removing a damaged layer by using potassium hydroxide KOH alkaline solution, texturing, and cleaning by RCA to obtain a silicon substrate 101;
(2) B as passivation layer and doping source layer is deposited on the surface of silicon wafer by ALD 2 O 3 Layer 102, B 2 O 3 The thickness of the layer is 5nm, and the deposition temperature is 150 ℃;
(3) At B 2 O 3 Deposition of Al on a layer 2 O 3 Layer 103, prepared by PECVD method, with thickness of 15nm and deposition temperature of 200deg.C;
(4) At Al 2 O 3 Deposition of SiN on a layer x Layer 104, prepared by PECVD method, with thickness of 55nm and deposition temperature of 200deg.C;
(5) Annealing in a strand sintering furnace, wherein the peak temperature is 750 ℃;
(6) Slotting and local p-type doping are realized by picosecond laser technology. B under the action of laser beam 2 O 3 The dopant source layer diffuses to the local melted Si surface and the fenestration area forms a front field/back field 105 by local B doping.
Through the steps to form B 2 O 3 /Al 2 O 3 /SiN x The laminated passivation film, as shown in FIG. 1B, has good surface passivation performance and dark saturation current density J 0 ＝5fA/cm 2 Local boron doping p at slotting + Back surface field contact resistance ρ c ＝2.0×10 -5 Ω.cm 2 And dark saturation current density J 0 ＝400fA/cm 2 。
Example 2
The embodiment provides a method with the step B 2 O 3 /Al 2 O 3 /SiN x A solar cell structure of laminated passivation film structure and a method of fabricating the same. The preparation process flow and structure of the solar cell provided in this embodiment are shown in fig. 2A and 2B, respectively, where the front side of the cell adopts an n-type doped emitter and a corresponding passivation film based on a p-type PERC cell, and the back side adopts the B described in embodiment 1 2 O 3 /Al 2 O 3 /SiN x And laminating passivation films, wherein the front and back surfaces of the battery respectively adopt grid-line silver and aluminum electrodes. The preparation method of the crystalline silicon battery specifically comprises the following steps:
(1) Selecting a p-type silicon substrate 201, removing a surface damage layer by adopting NaOH corrosion, and preparing a pyramid suede by using a diluted KOH solution;
(2) After RCA cleaning, phosphorus is diffused in a tube furnace to prepare an n-type emitter 202, wherein the diffusion temperature is 780 ℃, and the square resistance is about 100 ohm/sq;
(3) Removing surface phosphosilicate glass by using a dilute hydrofluoric acid solution, and removing a back n-type emitter and pyramid suede by using single-sided alkali polishing;
(4) Deposition of B on the backside using ALD 2 O 3 Layer 203, which serves as a passivation layer and also as a dopant source layer B 2 O 3 The thickness of the layer is 6nm, and the deposition temperature is 150 ℃;
(5) Deposition of Al on the backside using ALD 2 O 3 Layer 204, 10nm thick, deposition temperature 200 ℃;
(6) Deposition of SiN on front and back surfaces by PECVD x Layers 205, 206, 75nm and 55nm thick, respectively, at a deposition temperature of 400 ℃;
(7) Laser backside grooving and p-forming + A local back field 207 for hole collection;
(8) Preparing a metal aluminum electrode 208 by screen printing on the back surface, and designing a grid linear distributed electrode pattern;
(9) Preparing a metal silver electrode 209 on the front surface by screen printing, and designing a grid linear distributed electrode pattern;
(10) High-temperature sintering of belt furnace, front silver paste burning through SiN x And n + Ohmic contacts are formed for electron collection.
Example 3
The embodiment provides a method with the step B 2 O 3 /Al 2 O 3 /SiN x A tunneling silicon oxide passivation contact back junction (TOPCon-BJ) crystalline silicon cell structure of a laminated passivation film structure and a method for fabricating the same. The preparation process flow and structure of the TOPCon-BJ solar cell provided in this embodiment are shown in FIG. 3A and FIG. 3B, respectively, the front surface of the cell adopts the laminated passivation film described in embodiment 1, and the back surface adopts ultrathin SiO based on the TOPCon cell 2 An electron selective transport layer of n-type heavily doped polysilicon is superimposed, and Al is sequentially deposited on the transport layer 2 O 3 Layer and SiN x And the front and the back of the battery are respectively provided with a grid-line silver electrode and a silver-aluminum composite electrode. Preparation method of TOPCON-BJ batteryThe method comprises the following steps:
(1) Selecting a p-type silicon substrate 301, removing a surface damage layer by adopting NaOH corrosion, and preparing a pyramid suede by using a diluted KOH solution;
(2) Removing the back pyramid suede by single-sided alkali polishing;
(3) Deposition of ultra-thin SiO on the backside using PECVD process 2 Layer 302, phosphorus doped polysilicon 303, siO 2 The thickness is 1.5nm, and the thickness of the polysilicon is 150nm;
(4) At N 2 Medium annealing for 30 minutes at 850 ℃ to activate TOPCO structure;
(5) Deposition of B on front side using ALD 2 O 3 Layer 304, which serves as a passivation layer and also as a dopant source layer, B 2 O 3 The thickness of the layer is 8nm, and the deposition temperature is 150 ℃;
(6) Deposition of Al on the front and back surfaces by PECVD process 2 O 3 Layers 305, 306, 15nm thick, deposition temperature 200 ℃;
(7) Deposition of SiN on front and back surfaces by PECVD x Layers 307, 308, 55nm and 100nm thick, respectively, deposition temperature 400 ℃;
(8) Front-side windowing and p-forming by laser technology + A local top field 309 for hole collection;
(9) Preparing a metal aluminum electrode 310 on the front surface by screen printing, and designing a grid linear distributed electrode pattern;
(10) Preparing a metal silver-aluminum composite electrode 311 by screen printing on the back surface, and designing a grid linear distributed electrode pattern;
(11) High-temperature sintering of belt furnace, and burning through SiN of silver-aluminum composite slurry on back x And n + The polysilicon forms an ohmic contact for electron collection.
Example 4
The embodiment provides a method with the step B 2 O 3 /Al 2 O 3 /SiN x A tunneling silicon oxide passivation contact interdigital back contact (TOPCon-IBC) cell structure of stacked passivation film structure and its preparation method are provided. The preparation process flow and structure of the TOPCon-IBC solar cell provided by the embodiment are shown in FIG. 4A and FIG. 4B respectivelyThe front side of the cell used the laminated passivation film described in example 1 and the back side used the ultra-thin SiO based TOPCon cell 2 An electron selective transport layer of n-type heavily doped polysilicon is stacked, the transport layer having two selectively etched partial TOPCon regions, the transport layer and the selectively etched partial TOPCon regions being deposited with the stacked passivation film for a crystalline silicon solar cell described in example 1; the back of the battery adopts a grid linear silver electrode and a silver-aluminum composite electrode which are interdigital positive and negative electrodes, and the preparation method is as follows:
(1) A p-type polished silicon substrate 401 is selected, and the silicon substrate is cleaned;
(2) Double sided thermal growth of 1.5nm SiO 2 Layer 402;
(3) A 225nm thick phosphorus doped polysilicon layer 403 is double-sided deposited using an LPCVD process;
(4) At N 2 A TOPCon structure is activated at a high temperature of 900 ℃ in the tube furnace;
(5) Selectively etching away TOPCON region of back surface portion by laser or lithography technique, which region is left for preparation of p later + A back surface field;
(6) PECVD deposition of silicon nitride on the back phosphorus doped polysilicon layer is used for hydrogenating the gain passivation effect of polysilicon on one hand, and is used as a mask at the rear end during the front end texturing step on the other hand to prevent the back polysilicon from reaction decomposition;
(7) Annealing at 425 ℃ for 30 min to achieve SiN x Hydrogenating the polysilicon;
(8) Removing SiO at front end by NaOH alkali liquor 2 Heavily doped polysilicon and a surface damaged layer, and then preparing pyramid suede at the front end by using a diluted KOH solution;
(9) Removal of backside SiN with hydrofluoric acid buffer solution x A layer;
(10) Double sided sequential deposition 5nmB using ALD 2 O 3 Layers 404 and 7nmAl 2 O 3 Layer 405, deposited at 150 ℃ and 200 ℃, respectively;
(11) Double-sided deposition of 100nmSiN using PECVD technique x Layer 406, deposited at 200 ℃;
(12) Annealing in nitrogen-hydrogen mixed gas, wherein the annealing temperature is 450 ℃, and the annealing time is 20 minutes;
(13) The window is opened by ultraviolet pulse laser, the wavelength of the laser is 355nm, and the energy flux is 0.1J/cm 2 . Laser is applied to B 2 O 3 Preparation of boron doped p on the layer + A local back field 407;
(14) Manufacturing a separation electrode, p + The back field area is screen printed with an aluminum electrode 408, the emitter area is screen printed with a silver-aluminum composite electrode 409, and high-temperature sintering is performed by regulating and controlling a proper temperature;
(15) And removing the back field region and the emitter region contact electrode by using a specific process to form the interdigital positive and negative electrodes.
The above embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The preparation method of the laminated passivation film for the crystalline silicon solar cell is characterized by comprising the following steps of: the method comprises the following steps:
(1) Depositing B on the surface of a cleaned crystalline silicon substrate 2 O 3 Layer B of 2 O 3 The layer is prepared by ALD;
(2) At said B 2 O 3 Sequentially depositing a passivation film cover layer and a hydrogen-containing cover layer on the layer to form a laminated passivation film;
(3) Slotting on the laminated passivation film by picosecond laser technology to form molten state on at least part of silicon surface at slotting position, and to enable the B to be formed 2 O 3 The layer diffuses into the partially melted silicon surface as a boron dopant source, forming a p-type heavy doping.
2. The method for producing a laminated passivation film for a crystalline silicon solar cell according to claim 1, characterized in that: the B is 2 O 3 The deposition thickness of the layer is 1-50 nm.
3. The method for producing a laminated passivation film for a crystalline silicon solar cell according to claim 1, characterized in that: the passivation film cover layer comprises Al 2 O 3 、TiO 2 、Ga 2 O 3 、Ta 2 O 5 One or more of the passivation film cover layers are deposited by ALD or PECVD, and the deposition thickness is 5-100 nm.
4. The method for producing a laminated passivation film for a crystalline silicon solar cell according to claim 1, characterized in that: the hydrogen-containing cap layer comprises SiN x 、SiO x 、SiC x One or more of the hydrogen-containing cover layers is deposited by PECVD, and the deposition thickness is 10-200 nm.
5. A laminated passivation film for a crystalline silicon solar cell is characterized in that: a method for preparing a laminated passivation film for a crystalline silicon solar cell as defined in any one of claims 1 to 4, comprising sequentially depositing: the B is 2 O 3 A layer; the passivation film cover layer; the hydrogen-containing cap layer; and p-type local doping is realized by utilizing a laser technology.
6. The laminated passivation film for crystalline silicon solar cells according to claim 5, wherein: the passivation film cover layer is Al 2 O 3 The hydrogen-containing cover layer is SiN x 。
7. The preparation method of the crystalline silicon solar cell is characterized by comprising the following steps of: a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 is used for the production.
8. The method for manufacturing a crystalline silicon solar cell according to claim 7, wherein: the method comprises the following steps:
(1) Selecting a p-type silicon substrate and texturing;
(2) Preparing an n-type doped emitter and a corresponding passivation film of a p-type PERC-based battery on the front surface of the battery;
(3) Preparing a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 on the back surface of the cell;
(4) Preparing a metal silver electrode on the front side of the battery, preparing a metal aluminum electrode on the back side of the battery, performing high-temperature sintering, and burning through SiN with front silver paste x And n + Ohmic contacts are formed for electron collection and back aluminum electrodes are used for collecting holes.
9. The method for manufacturing a crystalline silicon solar cell according to claim 7, wherein: the method comprises the following steps:
(1) Selecting a p-type silicon substrate and texturing;
(2) Preparation of ultra-thin SiO based TOPCON cells on the cell backside 2 Superposing an electron selective transmission layer of n-type heavily doped polysilicon and a corresponding passivation film;
(3) Preparing a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 on the front surface of the cell;
(4) Preparing a metal aluminum electrode on the front side of the battery, preparing a silver aluminum composite electrode on the back side of the battery, performing high-temperature sintering, and burning through SiN by using silver aluminum composite slurry on the back side x And n + Ohmic contacts are formed for electron collection.
10. The method for manufacturing a crystalline silicon solar cell according to claim 7, wherein: the method comprises the following steps:
(1) Selecting a p-type polished silicon substrate;
(2) Preparation of ultra-thin SiO based TOPCON cells on the cell backside 2 Superposing an electron selective transmission layer of n-type heavily doped polysilicon;
(3) Preparing a laminated passivation film for a crystalline silicon solar cell according to any one of claims 5 to 6 on the front surface and the back surface of the cell;
(4) Manufacturing a separation electrode, screen printing an aluminum electrode in a p-type region, screen printing a silver-aluminum composite electrode in an n-type emitter region, and regulating and controlling a proper temperature to perform high-temperature sintering;
(5) And removing the back field region and the emitter region contact electrode by using a specific process to form the interdigital positive and negative electrodes.
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