CN109728104A - Cell piece passivation layer intermediate, solar battery sheet and preparation method thereof - Google Patents
Cell piece passivation layer intermediate, solar battery sheet and preparation method thereof Download PDFInfo
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- CN109728104A CN109728104A CN201811557004.4A CN201811557004A CN109728104A CN 109728104 A CN109728104 A CN 109728104A CN 201811557004 A CN201811557004 A CN 201811557004A CN 109728104 A CN109728104 A CN 109728104A
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- aluminium oxide
- passivation layer
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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
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Abstract
The present invention provides a kind of cell piece passivation layer intermediates, solar battery sheet and preparation method thereof, passivation layer intermediate involved in it includes the aluminium oxide counterdie and aluminium oxide outer membrane for being sequentially deposited to silicon chip back side, and hydroxyl is rich in aluminium oxide counterdie, structure based on passivation layer intermediate provided by the present invention, in specific solar battery sheet application scenarios, the passivation layer formed after annealing by it can play preferable passivation effect, it can also avoid penetrating after hydroxyl is heated in annealing process and destroy passivation layer outer surface, so that cell piece has preferable comprehensive performance.
Description
Technical field
The present invention relates to solar cell design field field more particularly to a kind of cell piece passivation layer intermediates, the sun
Energy cell piece and preparation method thereof.
Background technique
PERC battery is a kind of novel high performance solar batteries, and silicon chip back side is usually provided with one layer of aluminum oxide film
Film, the field-effect of aluminium oxide, which can be formed silicon chip surface, to be passivated, and can so effectively improve the minority carrier life time of silicon wafer.
It is made currently, aluminum oxide film generallys use Atomic layer deposition method, a kind of specific molding work of aluminum oxide film
Skill are as follows: silicon wafer is placed in atomic layer deposition apparatus, trimethyl aluminium and water are repeatedly passed through with impulse form circulation, will have been deposited
Silicon wafer after is annealed.During this, the intermediate product of trimethyl aluminium and water reaction generation has been generally rich in hydroxyl
Base, in annealing process, part of hydroxyl can release hydrogen ion, these hydrogen ions can be passivated the dangling bonds (hydrogen of silicon chip surface
Passivation), recombination-rate surface is reduced, and then can be further improved the incident photon-to-electron conversion efficiency of solar battery；So annealed
Cheng Zhong, some hydroxyl can generate H2 or H2O, H2 or H2O under high temperature sintering and lose in gaseous form, so
Aluminum oxide film can be penetrated and be destroyed, and influences the comprehensive performance of solar energy.
In consideration of it, it is necessary to provide a kind of technical solutions for solving prior art problem.
Summary of the invention
The present invention is directed at least solve one of technical problem of the existing technology, for achieving the above object, this hair
Bright to provide a kind of cell piece passivation layer intermediate, specific design method is as follows.
A kind of cell piece passivation layer intermediate, the passivation layer intermediate include the aluminium oxide for being sequentially deposited to silicon chip back side
Counterdie and aluminium oxide outer membrane, the aluminium oxide counterdie is interior to be rich in hydroxyl.
Further, the thickness range of the aluminium oxide counterdie is 4-8nm, and the thickness range of the aluminium oxide outer membrane is 4-
8nm。
Further, the thickness of the aluminium oxide counterdie and aluminium oxide outer membrane is 6nm.
The present invention also provides a kind of solar battery sheet, which includes silicon wafer, and the silicon chip back side is also
It is provided with passivation layer, the passivation layer is formed by the annealed processing of above-described passivation layer intermediate.
Further, the solar battery sheet further includes the silicon nitride layer for being deposited on the passivation layer surface.
The present invention also provides a kind of preparation method of solar battery sheet, which includes:
Passivation layer intermediate forming step, silicon wafer is placed in atomic layer deposition apparatus, is first with trimethyl aluminium and water
Presoma is presoma in aluminium oxide rich in the aluminium oxide counterdie for having hydroxyl, then using trimethyl aluminium and ozone in silicon chip back side formation
Counterdie surface forms aluminium oxide outer membrane, and the aluminium oxide counterdie and the aluminium oxide outer membrane constitute the passivation layer intermediate；
Passivation layer forming step makes annealing treatment the silicon wafer so that the passivation layer intermediate is shaped to passivation layer.
Further, when forming the aluminium oxide counterdie, the reaction cavity temperature of the atomic layer deposition apparatus is 220-300
DEG C, pressure 2-6mbar, the aluminium oxide counterdie forming process includes 20-40 subatom layer deposition cycle, one single deposition circulation
It successively include: nitrogen purging, the deionized water pulse of 40-80s and the 60- of the trimethyl aluminium pulse of 40-80s, 60-140s
140s nitrogen purging；Wherein, trimethyl aluminium pulse and the equal nitrogen buffer gas of deionized water pulse, carrier gas flux 150-
The flow of 250sccm, each nitrogen purging are 800-1200sccm.
Further, when forming the aluminium oxide outer membrane, the reaction cavity temperature of the atomic layer deposition apparatus is 220-300
DEG C, pressure 2-6mbar, the aluminium oxide outer membrane forming process includes 20-40 subatom layer deposition cycle, one single deposition circulation
It successively include: nitrogen purging, the ozone purge of 40-80s and the 60-140s nitrogen of the trimethyl aluminium pulse of 40-80s, 60-140s
Air-blowing is swept；Wherein, trimethyl aluminium pulse nitrogen buffer gas, carrier gas flux 150-250sccm, the flow of each ozone purge
Flow for 80-120sccm, each nitrogen purging is 800-1200sccm.
Further, the temperature of the annealing is 450-550 DEG C, pressure 1400-1800mtorr, and nitrogen flow is
1600-2400sccm, time 400-800s.
Further, the preparation method also has in the passivation layer surface cvd nitride after passivation layer forming step
The silicon nitride layer forming step of silicon.
The beneficial effects of the present invention are: the structure based on passivation layer intermediate provided by the present invention, in specific solar-electricity
In the piece application scenarios of pond, the passivation layer formed after annealing by it can play preferable passivation effect, additionally it is possible to avoid annealed
Passivation layer outer surface is penetrated and destroys after hydroxyl is heated in journey, so that cell piece has preferable comprehensive performance.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 show the schematic cross-section that silicon chip surface in the present invention is deposited with cell piece passivation layer intermediate；
Fig. 2 show a kind of schematic cross-section of solar battery sheet of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention relates to a kind of 200 ' of cell piece passivation layer intermediate, refering to what is shown in Fig. 1,200 ' of passivation layer intermediate includes
It is sequentially deposited to 22 ' of 21 ' of aluminium oxide counterdie and aluminium oxide outer membrane at 100 back side of silicon wafer, wherein be rich in 21 ' of aluminium oxide counterdie
Hydroxyl.
Refering to what is shown in Fig. 2, the present invention also provides a kind of solar battery sheets, and in the specific implementation process, the solar energy
Cell piece can be PERC battery or other type cells.Solar battery sheet includes silicon wafer 100, and 100 back side of silicon wafer is also set up
There is passivation layer 200, passivation layer 200 is formed by above annealed processing of 200 ' of passivation layer intermediate.It is specific as shown in the figure, it is blunt
Changing layer 200 includes the first passivation layer 21 and the second passivation layer 22, wherein the first passivation layer 21 and the second passivation layer 22 are respectively by oxygen
It is formed after changing 21 ' of aluminium counterdie and 22 ' of aluminium oxide outer membrane annealing.
Annealing in the present invention can activate the passivation effect of aluminium oxide, specifically in annealing process, oxidation
Layer of silicon dioxide film is formd between aluminium and silicon wafer 100, and activates the field-effect of aluminium oxide.Specifically, annealing
Afterwards, the silicon in silicon wafer can capture oxygen atom from aluminium oxide, so that it is thin to form one layer of silica in silicon wafer/aluminium oxide interface
Film；Since oxygen atom is seized, the lone pair electrons for originally belonging to oxygen atom have been left in aluminium oxide, and it is aobvious that this allows for aluminium oxide
Reveal elecrtonegativity, interface is formed an electric field, which can repel electronics, make electronics far from interface, to reduce boundary
Face is compound, achievees the effect that promote minority carrier life time, has fully ensured that the passivation effect of aluminium oxide.
Moreover, being rich in the characteristic of hydroxyl, after the annealing process, aluminium oxide counterdie based on 21 ' of aluminium oxide counterdie in the present invention
Part of hydroxyl in 21 ' can be converted into hydrogen ion, these hydrogen ions can be in conjunction with 100 surface dangling bonds of silicon wafer, to realize
Hydrogen passivation.Passivation layer 200 involved in such solar battery sheet of the present invention is equivalent to dual passivation effect, dual blunt
Changing effect makes solar battery sheet have more excellent incident photon-to-electron conversion efficiency.
Further, since 22 ' of aluminium oxide outer membrane in 200 ' of passivation layer intermediate is not present hydroxyl, after annealing, no
H2 or H2O can be generated, and can prevent the H2 or H2O that generate in 21 ' of aluminium oxide counterdie from penetrated in gaseous form to passivation layer 200
Surface, ensure that the integrality on 200 surface of passivation layer, to effectively improve the comprehensive performance of solar battery sheet.
In specific implementation process of the present invention, the thickness range of 21 ' of aluminium oxide counterdie is 4-8nm, 22 ''s of aluminium oxide outer membrane
Thickness range is 4-8nm.Wherein 21 ' of aluminium oxide counterdie and the thickness of 22 ' of aluminium oxide outer membrane are equal as a preferred implementation manner,
For 6nm.
It is shown with reference to Fig. 2, solar battery sheet involved in the present invention further includes being deposited on 200 surface of passivation layer
Silicon nitride layer 300.Wherein, the thickness range of silicon nitride layer 30 is usually 80-150nm, preferably 100nm.
Solar battery sheet according to the present invention also has the structures such as front electrode, rear electrode, specifically refers to existing
There is design, is not unfolded one by one herein.
The present invention also provides a kind of preparation method of solar battery sheet, which includes:
Passivation layer intermediate forming step, silicon wafer 100 is placed in atomic layer deposition apparatus (not shown), first with
Trimethyl aluminium and water are that presoma is formed at 100 back side of silicon wafer rich in 21 ' of aluminium oxide counterdie for having hydroxyl, then with trimethyl aluminium and
Ozone is presoma in the formation of 21 surface ' of aluminium oxide counterdie 22 ' of aluminium oxide outer membrane, 21 ' of aluminium oxide counterdie and 22 ' of aluminium oxide outer membrane
Constitute passivation layer intermediate；
Passivation layer forming step, annealing are deposited with the silicon wafer 100 of 200 ' of passivation layer intermediate so that among passivation layer
200 ' of body is shaped to passivation layer 200.
When forming 21 ' of aluminium oxide counterdie and 22 ' of aluminium oxide outer membrane in the present invention, temperature in the reaction chamber of atomic layer deposition apparatus
It is 2-6mbar that it is 220-300 DEG C that degree, which controls, pressure controls.
Wherein, the technological parameter of 21 ' of aluminium oxide counterdie is formed with reference to shown in following aluminium oxide counterdie molding technique parameter table,
21 ' forming process of aluminium oxide counterdie includes 20-40 subatom layer deposition cycle, and one single deposition circulation successively includes: 40-80s's
Trimethyl aluminium pulse, the nitrogen purging of 60-140s, the deionized water pulse of 40-80s and 60-140s nitrogen purging；Wherein,
Trimethyl aluminium pulse and the equal nitrogen buffer gas of deionized water pulse, carrier gas flux 150-250sccm, each nitrogen purging
Flow is 800-1200sccm.
More specifically, in the above 21 each circulation of ' moulding process of aluminium oxide counterdie: trimethyl aluminium pulse process is nitrogen
Gas carries trimethyl aluminium and generates chemisorption until saturation on surface to be deposited, and forms a monolayer；First step nitrogen
Purge is for removing the trimethyl aluminium and other by-products that are not associated in reaction chamber；Deionized water pulse process be go from
Sub- water and trimethyl aluminium, which generate, to be chemically reacted and forms Al2O3Monofilm；Second step nitrogen purge is unbonded for removing
Deionized water, to complete a deposition cycle.Based on process above parameter, when 21 ' of aluminium oxide counterdie is formed, one single deposition is followed
The film forming thickness range substantially 0.2nm of ring；And it is formed by 21 ' of aluminium oxide counterdie rich in hydroxyl.
Aluminium oxide counterdie molding technique parameter table
In addition, the technological parameter for forming 22 ' of aluminium oxide outer membrane refers to shown in following aluminium oxide outer membrane molding technique parameter table,
22 ' forming process of aluminium oxide outer membrane includes 20-40 subatom layer deposition cycle, and one single deposition circulation successively includes: 40-80s's
Trimethyl aluminium pulse, the nitrogen purging of 60-140s, the ozone purge of 40-80s and 60-140s nitrogen purging；Wherein, front three
Base aluminium pulse nitrogen buffer gas, carrier gas flux 150-250sccm, the flow of each ozone purge are 80-120sccm, often
The flow of secondary nitrogen purging is 800-1200sccm.
More specifically, in the above 22 each circulation of ' technique of aluminium oxide outer membrane: trimethyl aluminium pulse process is taken for nitrogen
Band trimethyl aluminium generates chemisorption until saturation on surface to be deposited, and forms a monolayer；First step nitrogen purging
Process is for removing the trimethyl aluminium and other by-products that are not associated in reaction chamber；Ozone purge process is ozone and trimethyl
Aluminium, which generates, to be chemically reacted and forms Al2O3 monofilm；Second step nitrogen purge be for removing unbonded ozone molecule,
To complete a deposition cycle.Based on process above parameter, when 22 ' of aluminium oxide outer membrane is formed, one single deposition circulation at film thickness
Spend range substantially 0.2nm.
Aluminium oxide outer membrane molding technique parameter table
21 ' of aluminium oxide counterdie and 22 ' of aluminium oxide outer membrane is that gradually depositing operation forms using monoatomic layer in the present invention,
It is suitble to low temperature depositing, the thickness uniformity possessed, density of film are conducive to the comprehensive performance for improving solar battery sheet.
As a preferred embodiment of the invention, 21 ' of aluminium oxide counterdie includes with 22 ' forming process of aluminium oxide outer membrane
30 subatom layer deposition cycle.Wherein, one single deposition circulation successively includes: the trimethyl aluminium of 60s when forming 22 ' of aluminium oxide outer membrane
Pulse, the nitrogen purging of 100s, the deionized water pulse of 60s and 100s nitrogen purging；Trimethyl aluminium pulse and deionized water
Pulse nitrogen buffer gas, carrier gas flux 200sccm, the flow of each nitrogen purging is 1000sccm.It is formed outside aluminium oxide
When 22 ' of film, one single deposition circulation successively include: the trimethyl aluminium pulse of 60s, the nitrogen purging of 100s, 60s ozone purge with
And 100s nitrogen purging；Trimethyl aluminium pulse nitrogen buffer gas, carrier gas flux 200sccm, the flow of each ozone purge
Flow for 100sccm, each nitrogen purging is 100sccm.
There is the aluminium oxide of aluminium oxide counterdie 21 ' and the 6nm thickness of 6nm thickness through 200 ' of passivation layer intermediate made from the technique
22 ' of outer membrane.After annealing, the thickness of the first passivation layer 21 and the second passivation layer 22 is also 6nm.
In the specific implementation process, annealing temperature involved in the present invention is 450-550 DEG C, pressure 1400-
1800mtorr, nitrogen flow 1600-2400sccm, time 400-800s.
In addition, the preparation method of solar battery sheet also has in passivation layer after passivation layer forming step in the present invention
The silicon nitride layer forming step of 200 surface deposited silicon nitrides.Silicon nitride layer forming step in this specific embodiment is set in PECVD
Standby middle progress, a kind of specific process parameter are as follows: radio-frequency power 1200-1800w, reaction chamber temperature are 450-550 DEG C, react
Chamber pressure is 1400-1800mttor, ammonia flow 5000-7000sccm, silane flow rate 800-1200sccm.
Of course, it should be understood that in other embodiments of the present invention, the molding parameter of silicon nitride layer 300 can also be unlimited
In parameter enumerated above；It can also be made of multilayered structure, and every layer of technological parameter can be different.In this specific implementation
In example, 200 annealing process step of passivation layer involved in solar battery sheet preparation process is carried out in PECVD device.
It should be appreciated that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should will say
As a whole, the technical solution in each embodiment may also be suitably combined to form those skilled in the art can for bright book
With the other embodiments of understanding.
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically
Protection scope bright, that they are not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention
Or change should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of cell piece passivation layer intermediate, which is characterized in that the passivation layer intermediate includes being sequentially deposited to silicon wafer back
The aluminium oxide counterdie and aluminium oxide outer membrane in face, the aluminium oxide counterdie is interior to be rich in hydroxyl.
2. cell piece passivation layer intermediate according to claim 1, which is characterized in that the thickness model of the aluminium oxide counterdie
It encloses for 4-8nm, the thickness range of the aluminium oxide outer membrane is 4-8nm.
3. cell piece passivation layer intermediate according to claim 2, which is characterized in that the aluminium oxide counterdie and aluminium oxide
The thickness of outer membrane is 6nm.
4. a kind of solar battery sheet, including silicon wafer, which is characterized in that the silicon chip back side is additionally provided with passivation layer, described blunt
Change the annealed processing molding of layer passivation layer intermediate as described in claim 1-3 any one.
5. solar battery sheet according to claim 4, which is characterized in that the solar battery sheet further includes being deposited on
The silicon nitride layer of the passivation layer surface.
6. a kind of preparation method of solar battery sheet characterized by comprising
Passivation layer intermediate forming step, silicon wafer is placed in atomic layer deposition apparatus, is first forerunner with trimethyl aluminium and water
Body is presoma in aluminium oxide counterdie rich in the aluminium oxide counterdie for having hydroxyl, then using trimethyl aluminium and ozone in silicon chip back side formation
Surface forms aluminium oxide outer membrane, and the aluminium oxide counterdie and the aluminium oxide outer membrane constitute the passivation layer intermediate；
Passivation layer forming step makes annealing treatment the silicon wafer so that the passivation layer intermediate is shaped to passivation layer.
7. the preparation method of solar battery sheet according to claim 6, which is characterized in that form the aluminium oxide counterdie
When, the reaction cavity temperature of the atomic layer deposition apparatus is 220-300 DEG C, pressure 2-6mbar, the aluminium oxide counterdie shape
It include 20-40 subatom layer deposition cycle at process, one single deposition circulation successively includes: trimethyl aluminium pulse, the 60- of 40-80s
Nitrogen purging, the deionized water pulse of 40-80s and the 60-140s nitrogen purging of 140s；Wherein, trimethyl aluminium pulse with go
The equal nitrogen buffer gas of ion aquapulse, carrier gas flux 150-250sccm, the flow of each nitrogen purging is 800-
1200sccm。
8. the preparation method of solar battery sheet according to claim 6 or 7, which is characterized in that form the aluminium oxide
When outer membrane, the reaction cavity temperature of the atomic layer deposition apparatus is 220-300 DEG C, pressure 2-6mbar, outside the aluminium oxide
Film forming process includes 20-40 subatom layer deposition cycle, and one single deposition circulation successively includes: the trimethyl aluminium arteries and veins of 40-80s
Punching, the nitrogen purging of 60-140s, the ozone purge of 40-80s and 60-140s nitrogen purging；Wherein, trimethyl aluminium pulse with
Nitrogen is carrier gas, and carrier gas flux 150-250sccm, the flow of each ozone purge is 80-120sccm, each nitrogen purging
Flow be 800-1200sccm.
9. according to the preparation method of solar battery sheet as claimed in claim 6, which is characterized in that the temperature of the annealing is
450-550 DEG C, pressure 1400-1800mtorr, nitrogen flow 1600-2400sccm, time 400-800s.
10. the preparation method is in passivation according to the preparation method of solar battery sheet described in claim 6-9 any one
Also have in the silicon nitride layer forming step of the passivation layer surface deposited silicon nitride after formable layer step.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112563370A (en) * | 2020-12-04 | 2021-03-26 | 通威太阳能（安徽）有限公司 | Single crystal PERC crystal silicon cell back passivation preparation process and PERC solar cell |
| CN112838143A (en) * | 2020-12-31 | 2021-05-25 | 横店集团东磁股份有限公司 | Deposition method of aluminum oxide film in PERC battery |
| CN115132851A (en) * | 2021-08-26 | 2022-09-30 | 上海晶科绿能企业管理有限公司 | Solar cell, manufacturing method thereof and photovoltaic module |
| WO2022206789A1 (en) * | 2021-03-31 | 2022-10-06 | 通威太阳能（安徽）有限公司 | Solar cell, alox coating method therefor, cell back surface passivation structure, and method |
| CN115188833A (en) * | 2021-09-06 | 2022-10-14 | 上海晶科绿能企业管理有限公司 | Solar cell, manufacturing method thereof and photovoltaic module |
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Application publication date: 20190507 |