CN115425093A - Solar cell laminated passivation structure and preparation method thereof - Google Patents

Solar cell laminated passivation structure and preparation method thereof Download PDF

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CN115425093A
CN115425093A CN202110530123.6A CN202110530123A CN115425093A CN 115425093 A CN115425093 A CN 115425093A CN 202110530123 A CN202110530123 A CN 202110530123A CN 115425093 A CN115425093 A CN 115425093A
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layer
passivation
passivation layer
solar cell
silicon
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柳伟
皮埃尔·沃灵顿
陈奕峰
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Trina Solar Co Ltd
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    • 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
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    • 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 potential barriers
    • 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 potential barriers 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
    • H01L31/0682—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 homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868—Passivation
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Abstract

The invention discloses a solar cell laminated passivation structure and a preparation method thereof, wherein the laminated passivation structure comprises a first passivation layer, a second passivation layer and a third passivation layer which are sequentially and outwards arranged from the surface of the back surface of a solar cell silicon substrate, the third passivation layer contains hydrogen, the third passivation layer is selected from at least one of a titanium dioxide layer, a silicon dioxide layer, a titanium nitride layer and a silicon oxynitride layer, and the hydrogen content of the third passivation layer is 1e +20H/cm 3 ～1e+23H/cm 3 . The third passivation layer far away from the silicon substrate contains hydrogen with specific content, and the hydrogen can be injected into the surface and the interior of the silicon wafer in the subsequent annealing or sintering process to passivate the recombination center, so that the passivation effect is good, the open-circuit voltage of the cell is improved, and the performance of the solar cell is improved.

Description

Solar cell laminated passivation structure and preparation method thereof
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a solar cell laminated passivation structure and a preparation method thereof.
Background
Solar cells are devices that convert light energy into electrical energy through the photoelectric effect or the photochemical effect, and crystalline silicon solar cells that operate with the photovoltaic effect are the mainstream. In order to improve the efficiency of the crystalline silicon solar cell, the surface of the cell must be well passivated, and the recombination of surface defects is reduced so as to improve the open-circuit voltage of the cell. Currently, the most common back passivation technique for commercial PERC cells is a stacked passivation with layers of aluminum oxide and silicon nitride, and a passivation film of silicon nitride on the front side. CN111106183A deposits a silicon dioxide film layer on the back of the polished silicon wafer, then deposits a phosphorus-doped amorphous silicon carbide film layer, and carries out annealing treatment to convert the amorphous silicon carbide into microcrystalline silicon carbide. The back passivation structure of CN110112243A comprises a first silicon oxide film layer, an aluminum oxide passivation film layer, a first silicon nitride antireflection layer and a second silicon oxide film layer which are sequentially arranged outwards from the back of the solar cell silicon wafer substrate.
However, the passivation effect of the above method is not ideal, and the efficiency of the solar cell needs to be improved, so it is necessary to provide a solar cell stack passivation structure to improve the efficiency of the crystalline silicon solar cell.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a solar cell stack passivation structure and a method for manufacturing the same.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a solar cell stacked passivation structure, which comprises a first passivation layer, a second passivation layer and a third passivation layer, wherein the first passivation layer, the second passivation layer and the third passivation layer are sequentially arranged outwards from the surface of the back side of a solar cell silicon substrate, the third passivation layer contains hydrogen, and the third passivation layer is selected from titanium dioxide (TiO) 2 ) Layer, silicon dioxide (SiO) 2 ) Layer, titanium nitride layer (TiN), and silicon oxynitride (SiO) x N y Wherein x and y satisfy valence balance of the substance) layer, and the hydrogen content of the third passivation layer is 1e +20H/cm 3 ～1e+23H/cm 3 。
In the laminated passivation structure, the third passivation layer far away from the silicon substrate contains hydrogen with specific content, and the hydrogen can be injected into the surface and the interior of the silicon wafer in the subsequent annealing or sintering process to passivate the recombination center, so that the laminated passivation structure has a good passivation effect, the open-circuit voltage of the cell is improved, and the performance of the solar cell is further improved. Wherein, if the hydrogen content of the third passivation layer is too low, the composite center can not be passivated, so that the passivation effect is poor; too much hydrogen content can cause hydrogen to become recombination centers, introducing more defects.
It should be noted that, in the present invention, the first passivation layer, the second passivation layer, and the third passivation layer may be in direct contact in the above order, or another functional layer may be disposed between the first passivation layer and the second passivation layer, or another functional layer may be disposed between the second passivation layer and the third passivation layer, which is not limited in the present invention.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the thickness of the third passivation layer is 25nm to 150nm, such as 25nm, 30nm, 35nm, 40nm, 50nm, 60nm, 80nm, 85nm, 90nm, 100nm, 115nm, 125nm, 135nm, 150nm, etc., preferably 50nm to 80nm.
In the present invention, the third passivation layer may be a single layer or a stack of at least two layers. When a stack of at least two layers is formed, the thickness of the third passivation layer refers to the total thickness of the stack. Within the preferable thickness range, the good passivation effect can be ensured, and the applicability to the dual-glass assembly film system can be improved.
Preferably, the third passivation layer is a titanium dioxide layer, a silicon oxynitride layer, or a stack of a titanium dioxide layer and a silicon oxynitride layer. That is, the titanium oxide layer may be a single layer, the silicon oxynitride layer may be a single layer, or a stack of the two layers.
In the case of a laminate of a titanium oxide layer and a silicon oxynitride layer, the thickness ratio of titanium oxide to silicon oxynitride layer is preferably (1 to 2): 1, for example 1, 1.5.
Preferably, the first passivation layer is SiO 2 And (3) a layer.
Preferably, the thickness of the first passivation layer is 0.2nm to 5nm, such as 0.2nm, 0.5nm, 1nm, 1.5nm, 2nm, 2.5nm, 3nm, 4nm, or 5nm, and the like.
Preferably, the second passivation layer is an aluminum oxide layer.
Preferably, the thickness of the second passivation layer is 1nm to 30nm, such as 1nm, 3nm, 4nm, 5nm, 8nm, 10nm, 15nm, 18nm, 20nm, 25nm, 30nm, or the like.
The invention also provides a high-efficiency PERC solar cell, the structural schematic diagram of which is shown in figure 1, the PERC solar cell comprises a silicon substrate 1 (such as a P-type silicon substrate) and an emission junction region formed on the silicon substrate 1, the emission junction region comprises a heavy diffusion region 2 and a light diffusion region 3, and the front surface of the silicon substrate is provided with SiO sequentially 2 Film 4 and SiN x Antireflection layer 5, the silicon substrate openly still is provided with Ag electrode 6, ag electrode 6 links to each other with the transmission junction region, the silicon substrate back is provided with stromatolite passivation structure and Al electrode 7, al electrode 7 passes stromatolite passivation structure and local BSF p + +8 link to each other, stromatolite passivation structure includes by the surface at the solar cell silicon substrate back outwards setting in proper order first layer passivation layer 9, second floor passivation layer 10 and third passivation layer 11.
In a second aspect, the present invention provides a method for preparing a passivation structure of a solar cell stack according to the first aspect, the method comprising: and sequentially preparing a first passivation layer, a second passivation layer and a third passivation layer on the back of the silicon wafer with the p-n junction to obtain the laminated passivation structure.
Preferably, the method for preparing the first passivation layer includes any one of a thermal oxidation method, a wet method, or a Chemical Vapor Deposition (CVD) method.
Preferably, the method for preparing the second passivation Layer includes any one of a Plasma Enhanced Chemical Vapor Deposition (PECVD) method or an Atomic Layer Deposition (ALD) method.
Preferably, the method for preparing the third passivation Layer includes a Plasma Enhanced Chemical Vapor Deposition (PECVD) method, an Atomic Layer Deposition (ALD) method, magnetron sputtering, thermal evaporation, a Physical Vapor Deposition (PVD) method, or a Chemical Vapor Deposition (CVD) method, and when the thin film is prepared by the above method, a reaction gas contains a hydrogen element.
Compared with the prior art, the invention has the following beneficial effects:
in the laminated passivation structure, the third passivation layer far away from the silicon substrate contains hydrogen with specific content, and the hydrogen can be injected into the surface and the interior of the silicon wafer in the subsequent annealing or sintering process to passivate the recombination center, so that the laminated passivation structure has a good passivation effect, the open-circuit voltage of the cell is improved, and the performance of the solar cell is further improved.
Drawings
FIG. 1 is a schematic diagram of the structure of a PERC solar cell, 1-silicon substrate, 2-heavy diffusion region, 3-light diffusion region, 4-SiO 2 Film, 5-SiN x The anti-reflection layer, the 6-Ag electrode, the 7-Al electrode, the 8-BSF p + +, the 9-first passivation layer, the 10-second passivation layer and the 11-third passivation layer.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
This example provides a PERC solar cell, prepared by the following method:
(1) Removing the mechanical damage layer of the P-type silicon wafer by using 35g/L KOH solution for 3 microns, and then corroding the surface of the silicon wafer by using 15g/L NaOH solution to form a pyramid structure with the thickness of 2.5 microns.
(2) By using POCl 3 And diffusing by liquid low-pressure diffusion to form a p-n junction, wherein the diffusion temperature is 810 ℃, the process time is 90min, and the diffusion sheet resistance is controlled to be 130 ohm/sq.
(3) And (3) laser SE doping, wherein P atoms in the diffused phosphorosilicate glass are subjected to laser doping through high laser temperature to form a local heavily doped region, and the diffusion sheet resistance is 80ohm/sq.
(4) And removing the back junction by using a chain type cleaning machine, polishing the back surface of the silicon wafer by 3.5 mu m, and removing the peripheral p-n junction.
(5) Preparing a laminated passivation structure on the back of the silicon substrate obtained in the step (4):
oxidizing the silicon wafer obtained in the step (4) to generate thin SiO on the front surface, the back surface and the edge of the silicon wafer 2 Film, thickness 3nm.
Depositing Al on the back by PECVD method 2 O 3 And the thickness of the film is 20nm.
Depositing TiO on the back by PECVD method 2 Film, thickness 70nm, tiO 2 The hydrogen content in the film is 4e +21H/cm 3 。
(6) Positive SiN deposition by PECVD method x Film, thickness 85nm.
(7) And (3) adopting a 532nm ns laser to perform local grooving on the laminated film on the back surface, and opening the laminated passivation film.
(8) And printing back Al slurry after drying the printed back Ag electrode.
(9) And printing a front Ag electrode and quickly sintering at 875 ℃ to form good ohmic contact so as to obtain the solar cell.
(10) Test I-V and sort.
Example 2
This example provides a PERC solar cell, prepared by the following method:
(1) Removing the mechanical damage layer of the P-type silicon wafer by using 35g/L KOH solution for 3 microns, and then corroding the surface of the silicon wafer by using 15g/L NaOH solution to form a pyramid structure with the thickness of 3 microns.
(2) Using POCl 3 And diffusing by liquid low-pressure diffusion to form a p-n junction, wherein the diffusion temperature is 810 ℃, the process time is 90min, and the diffusion sheet resistance is controlled to be 160 ohm/sq.
(3) And (3) laser SE doping, wherein the P atoms in the diffused phosphorosilicate glass are subjected to laser doping through laser high temperature to form a local heavily doped region, and the diffusion sheet resistance is 95ohm/sq.
(4) And removing back junctions by using a chain type cleaning machine, polishing the back surface of the silicon wafer by 4 mu m, and removing peripheral p-n junctions.
(5) Preparing a laminated passivation structure on the back of the silicon substrate obtained in the step (4):
oxidizing the silicon wafer obtained in the step (4) to generate thin SiO on the front surface, the back surface and the edge of the silicon wafer 2 Film thickness 3nm.
Deposition of Al on the backside by ALD 2 O 3 And the thickness of the film is 5nm.
Sequentially depositing TiO on the back by PECVD method 2 Film and TiN film, the thickness of which is 35nm and 50nm respectively 2 The total hydrogen content in the film and TiN film is 6e +21H/cm 3 。
(6) Positive SiN deposition by PECVD method x Film, thickness 85nm.
(7) And (3) adopting a 532nm ns laser to perform local grooving on the laminated film on the back surface, and opening the laminated passivation film.
(8) And printing back Al paste after drying the printed back Ag electrode.
(9) Printing a front Ag electrode and rapidly sintering at 875 ℃ to form good ohmic contact so as to obtain the solar cell.
(10) Test I-V and sort.
Example 3
This example provides a PERC solar cell, prepared by the following method:
(1) Removing the mechanical damage layer of the P-type silicon wafer by using 35g/L KOH solution for 3 microns, and then corroding the surface of the silicon wafer by using 15g/L NaOH solution to form a pyramid structure with the thickness of 2 microns.
(2) Using POCl 3 And diffusing by liquid low-pressure diffusion to form a p-n junction, wherein the diffusion temperature is 810 ℃, the process time is 90min, and the diffusion sheet resistance is controlled to be 140 ohm/sq.
(3) And (3) laser SE doping, wherein P atoms in the diffused phosphorosilicate glass are subjected to laser doping through high laser temperature to form a local heavily doped region, and the diffusion sheet resistance is 70ohm/sq.
(4) And removing the back junction by using a chain type cleaning machine, polishing the back surface of the silicon wafer by 3 mu m, and removing the peripheral p-n junction.
(5) Preparing a laminated passivation structure on the back of the silicon substrate obtained in the step (4):
oxidizing the silicon wafer obtained in the step (4) to generate thin SiO on the front surface, the back surface and the edge of the silicon wafer 2 Film thickness 3nm.
Depositing Al on the back by PECVD method 2 O 3 And the thickness of the film is 20nm.
Deposition of TiO on the backside by PECVD 2 Film of 70nm thickness of TiO 2 The hydrogen content in the film is 5e +, 21H/cm 3 。
(6) SiN deposition on the front side by PECVD method x Film, thickness 85nm.
(7) And (3) adopting a 532nm ns laser to perform local grooving on the laminated film on the back surface, and opening the laminated passivation film.
(8) And printing back Al paste after drying the printed back Ag electrode.
(9) Printing a front Ag electrode and rapidly sintering at 875 ℃ to form good ohmic contact so as to obtain the solar cell.
(10) Test I-V and sort.
Example 4
The present embodiment is different from embodiment 1 only in step (5), and step (5) of the present embodiment is: preparing a laminated passivation structure on the back of the silicon substrate obtained in the step (4):
oxidizing the silicon wafer obtained in the step (4) to generate thin SiO on the front surface, the back surface and the edge of the silicon wafer 2 Film thickness 3nm.
Depositing Al on the back by PECVD method 2 O 3 And the thickness of the film is 20nm.
Deposition of SiO on the back by PECVD method x N y A thin film with a thickness of 60nm x N y The hydrogen content in the film is 5e +, 21H/cm 3 。
Example 5
The present embodiment differs from embodiment 1 only in step (5), and step (5) in the present embodiment is:
oxidizing the silicon wafer obtained in the step (4) to generate thin SiO on the front surface, the back surface and the edge of the silicon wafer 2 Film thickness 3nm.
Depositing Al on the back by PECVD method 2 O 3 And the thickness of the film is 20nm.
Depositing TiO on the back by PECVD method 2 A film with the thickness of 35nm and SiO deposited on the back surface by a PECVD method x N y Film, thickness 35nm, tiO 2 Film and SiO x N y The total hydrogen content in the film is 5e +21H/cm 3 。
In embodiments 1 to 5 of the present invention, since the passivation layer has a suitable hydrogen content, the passivation effect can be effectively improved, the open-circuit voltage of the cell can be increased, and the performance of the solar cell can be improved. Particularly, when the third passivation layer is a single layer of titanium dioxide or a lamination of titanium dioxide and a silicon oxynitride layer, the improvement effect is better.
Comparative example 1
This comparative example differs from example 1 in that TiO 2 The hydrogen content in the film is 1e +, 19H/cm 3 。
If the hydrogen content of the passivation layer is too low, the composite center can not be passivated, and the passivation effect is poor.
Comparative example 2
The comparative example differs from example 1 in that TiO 2 The hydrogen content in the film is 5e +23H/cm 3 。
If the hydrogen content of the passivation layer is too much, hydrogen becomes a recombination center, more defects are introduced, and the efficiency of the crystalline silicon solar cell is not improved favorably.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A solar cell lamination passivation structure is characterized in thatThe laminated passivation structure comprises a first passivation layer, a second passivation layer and a third passivation layer which are sequentially arranged outwards from the surface of the back side of a silicon substrate of the solar cell, wherein the third passivation layer contains hydrogen, the third passivation layer is selected from at least one layer of a titanium dioxide layer, a silicon dioxide layer, a titanium nitride layer and a silicon oxynitride layer, and the hydrogen content of the third passivation layer is 1e +20H/cm 3 ～1e+23H/cm 3 。
2. The solar cell stack passivation structure of claim 1, wherein the thickness of the third passivation layer is 25nm to 150nm.
3. The solar cell stack passivation structure according to any of claims 1-3, wherein the thickness of the third passivation layer is between 50nm and 80nm.
4. The solar cell stack passivation structure according to any one of claims 1 to 3, wherein the third passivation layer is a titanium dioxide layer, a silicon oxynitride layer, or a stack of a titanium dioxide layer and a silicon oxynitride layer.
5. The solar cell stack passivation structure of any one of claims 1-4, wherein the first passivation layer is SiO 2 A layer;
preferably, the thickness of the first passivation layer is 0.2nm to 5nm.
6. The solar cell stack passivation structure according to any of claims 1-5, wherein the second passivation layer is an aluminum oxide layer;
preferably, the thickness of the second passivation layer is 1nm to 30nm.
7. A method of fabricating a solar cell stack passivation structure according to any of claims 1-6, characterized in that the method comprises: and sequentially preparing a first passivation layer, a second passivation layer and a third passivation layer on the back of the silicon wafer with the p-n junction to obtain the laminated passivation structure.
8. The method of claim 7, wherein the first passivation layer is prepared by any one of a thermal oxidation method, a wet method or a chemical vapor deposition method.
9. The method according to claim 7 or 8, wherein the method for preparing the second passivation layer comprises any one of a plasma enhanced chemical vapor deposition method or an atomic layer deposition method.
10. The method according to any one of claims 7 to 9, wherein the third passivation layer is formed by a plasma enhanced chemical vapor deposition method, an atomic layer deposition method, magnetron sputtering, thermal evaporation, a physical vapor deposition method or a chemical vapor deposition method, and when the thin film is formed by the above method, the reaction gas contains hydrogen.
CN202110530123.6A 2021-05-14 2021-05-14 Solar cell laminated passivation structure and preparation method thereof Pending CN115425093A (en)

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