CN107245760A - The processing method of silicon chip of solar cell - Google Patents
The processing method of silicon chip of solar cell Download PDFInfo
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- CN107245760A CN107245760A CN201710324497.6A CN201710324497A CN107245760A CN 107245760 A CN107245760 A CN 107245760A CN 201710324497 A CN201710324497 A CN 201710324497A CN 107245760 A CN107245760 A CN 107245760A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/10—Etching in solutions or melts
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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Abstract
The present invention relates to a kind of processing method of silicon chip of solar cell：Chemical attack processing is carried out to silicon chip surface at 40 90 DEG C using aqueous slkali, to remove the damage layer of silicon chip surface；Silicon chip after processing is immersed into progress borehole processing in the first treatment fluid at 5 40 DEG C, then immerse in second processing liquid take off at 10 40 DEG C and wash noble metal processing, wherein, the first treatment fluid includes hydrofluoric acid, hydrogen peroxide, precious metal ion and water, and second processing liquid includes ammoniacal liquor and water；Treated silicon chip is immersed into the 3rd treatment fluid at 20 40 DEG C and carries out expanding treatment, the 3rd treatment fluid includes hydrofluoric acid, nitric acid and water；Immersion fourth process liquid after silicon chip washing after processing is subjected to moditied processing, fourth process liquid includes alkali and water；Treated silicon chip is immersed at 40 90 DEG C in the aqueous solution of hydrochloric acid and hydrogen peroxide to remove residual metal ions, then immerse in the aqueous solution of hydrofluoric acid and removed after oxide layer at 20 40 DEG C, washing, drying.
Description
Technical field
The present invention relates to crystal silicon solar batteries field, more particularly to a kind of processing method of silicon chip of solar cell.
Background technology
At present in crystal silicon solar batteries field, three kinds of relatively common crystal silicon matrix batteries are polycrystalline, monocrystalline, class list
Crystalline substance, silicon chip cutting mode it is relatively common be mortar cutting and Buddha's warrior attendant wire cutting.At present, it is used to prepare solar cell in processing
Silicon chip when, conventional polycrystalline typically takes the mode of sour making herbs into wool, forms vermiform pit-hole, the treated silicon chip surface of this method
Reflectivity is higher, but its photoelectric transformation efficiency is difficult to further lifting；Conventional single typically takes the mode of alkali making herbs into wool, forms gold
Word tower structure, its reflectivity is reduced significantly with respect to polycrystalline.
In terms of cost of manufacture, diamond wire cutting mode greatly reduces list, polycrystalline cutting cost, diamond wire list
Chip uses alkali making herbs into wool, can preferably carry out process choice and matching, and diamond wire multi-wafer uses conventional acid making herbs into wool, reflectivity
It is high and outward appearance has stria defect, have a strong impact on the photoelectric transformation efficiency of diamond wire multi-wafer.Due to class monocrystalline collect single, polycrystalline in
One, its photoelectric transformation efficiency is between list, polycrystalline in theory, but because its making herbs into wool scheme is limited, so never real
Existing large-scale production.
In addition, in terms of matte Preparation equipment, polycrystalline generally carries out sour making herbs into wool using chain type horizontal equipment, and monocrystalline is general
Carry out alkali making herbs into wool all over using slot type vertical equipment, not yet go out to be now able at present to realize using identical making herbs into wool mode to list, polycrystalline,
The all-in-one of class monocrystalline processing.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of processing method of silicon chip of solar cell, with
The problem of solving conventional single, polycrystalline or different class monocrystalline making herbs into wool mode, and improve crystal silicon solar batteries conversion efficiency.
The invention provides a kind of processing method of silicon chip of solar cell, comprise the following steps：
(1) 10-240s is handled to silicon chip surface chemical attack at 40-90 DEG C using aqueous slkali, to remove silicon chip surface
Damage layer；
(2) silicon chip after step (1) processing is immersed into borehole in the first treatment fluid at 5-40 DEG C and handles 50-240s, so
Immerse in second processing liquid take off at 10-40 DEG C afterwards and wash noble metal processing 10-200s, wherein, the first treatment fluid includes hydrogen
Fluoric acid, hydrogen peroxide, precious metal ion and water, second processing liquid include ammoniacal liquor and water；
(3) immersed after the silicon chip washing treated step (2) at 20-40 DEG C in the 3rd treatment fluid and carry out expanding treatment
20-200s, the 3rd treatment fluid includes hydrofluoric acid, nitric acid and water；
(4) by moditied processing 1-50s, fourth process in immersion fourth process liquid after the silicon chip washing after step (3) processing
Liquid includes alkali and water；
(5) the mixed of hydrochloric acid and aqueous hydrogen peroxide solution is immersed at 40-90 DEG C after the silicon chip washing treated step (4)
Close in solution, handle 50-240s, to remove residual metal ions, then washing immerses the water-soluble of hydrofluoric acid at 20-40 DEG C
50-240s is handled in liquid, with except oxide layer, washing, drying.
Further, in step (1), the crystal formation of silicon chip is monocrystalline, polycrystalline or class monocrystalline.
Further, in step (1), alkali is in sodium hydroxide, potassium hydroxide and TMAH (TMAH)
It is one or more of.
Further, in step (1), the mass fraction of alkali is 0.05-10% in aqueous slkali.
Further, in step (2), precious metal ion is one kind in gold ion, silver ion, platinum ion and palladium ion
Or it is several.
Further, in step (2), the concentration of precious metal ion is 1 × 10 in the first treatment fluid-6mol/L-5×10-2mol/L。
Further, in step (2), in step (2), the first treatment fluid also includes the first additive, the first addition
Agent is the one or more in polyacrylic acid, poly- D, Pfansteihl, polyvinyl alcohol and fluorocarbon surfactant.
Further, in step (2), the concentration of the first additive is 2-20ppm in the first treatment fluid.
Further, in step (2), the mass fraction of hydrofluoric acid is 5-20% in the first treatment fluid, hydrogen peroxide
Mass fraction is 0.1-10%.
Further, in step (2), the concentration of ammoniacal liquor is 0.1-20% in second processing liquid.
In step (2), in the first treatment fluid, hydrogen peroxide as oxidant, hydrofluoric acid as reducing agent, noble metal from
Son can form nanometer suede structure as catalyst, and each crystal orientation corrosion rate can be tended to be close by the first additive, so that
Make outward appearance crystalline substance flower performance more consistent.In second processing liquid, ammoniacal liquor can be with precious metal ion formation hydroxide diamino alloy, and it is
A kind of complex compound soluble in water, so as to reach the de- purpose for washing noble metal.
Further, in step (3), the 3rd treatment fluid also include Second addition, Second addition be polyvinyl alcohol,
Triethanolamine, tartaric acid, silane coupler, acrylic copolymer, fluorin modified crylic acid copolymer, poly dimethyl oxosilane and poly-
One or more in ether modified polydimethyl oxosilane.
Further, in step (3), the mass fraction of Second addition is 0.5-5% in the 3rd treatment fluid.
Further, in step (3), the mass fraction of hydrofluoric acid is 1-10%, the quality of nitric acid in the 3rd treatment fluid
Fraction is 10-40%.
In step (3), redox reaction occurs for nitric acid and hydrofluoric acid and silicon chip, can be further by nanometer suede structure
Expand, and Second addition plays a part of orientation and strengthens corrosion, thus it is possible to vary the depth-width ratio of hole.
Further, in step (4), alkali is sodium hydroxide or potassium hydroxide.In step (4), in fourth process liquid
The mass fraction of alkali is 0.01-5%.
Further, in step (4), fourth process liquid also include the 3rd additive, the 3rd additive be vinyl acetate,
Glucose, acrylic copolymer, 18- crown ethers -6,15- crown ethers -5,12- crown ethers -4, butyl glycol ether, butyl, third
One or more in glycol propyl ether, propylene glycol monomethyl ether, propandiol butyl ether, dipropylene glycol propyl ether and tripropylene glycol methyl ether.
Further, in step (4), the mass fraction of the 3rd additive is 0.001-1% in fourth process liquid.
The effect of the moditied processing of step (4) is to remove the rougher corner angle of silicon chip surface, in step (4), the work of alkali
With being to remove the porous silicon that is formed in (3) step, and the 3rd additive can remove corner angle in nanometer suede structure etc., make
Nanometer suede structure evenly with it is consistent.
Further, in step (5), the concentration of hydrochloric acid is 3-7% in mixed solution, and the concentration of hydrogen peroxide is 2-
5%.Hydrochloric acid, hydrogen peroxide and water are according to hydrochloric acid in mixed solution：Hydrogen peroxide：Water=1:1:The ratio mixing of (5-7), is referred to as
For a cleaning fluid, residual metal ions can be effectively removed.
Further, in step (5), the concentration of hydrofluoric acid is 4-8%.
In the present invention, aqueous slkali refers to the aqueous solution of alkali.
By such scheme, the present invention at least has advantages below：
Because the sour making herbs into wool of conventional polycrystalline is after processing silicon chip, its matte is micron scale construction, and sunken luminous effect is poor, reflectivity
Higher (20%~25%).And the making herbs into wool of conventional single alkali processing silicon chip after, although the reflectivity of silicon chip than it is relatively low (8%~
12%), but matte is still micron scale construction, specific surface area is smaller, the space of silver-silicon contact is limited, so as to have impact on
The further lifting of monocrystalline efficiency.Class monocrystalline integrates single, polycrystalline feature, it is difficult to suitable for acid or alkali process for etching,
During processing, had a greatly reduced quality in terms of photoelectric transformation efficiency.
Technical scheme is applied to monocrystalline, polycrystalline and class monocrystalline, and matrix selection is unrestricted, using the present invention's
Silicon chip handled by technique, its matte is nanoscale structures, and reflectivity is relatively low, and reflectivity even can tend to 0, in actual industrial
In production, the adjustment of reflectivity can be carried out according to actual needs, and the sunken luminous effect of silicon chip is not fully exerted, monocrystalline efficiency
Improve 0.3%~0.8%.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate detailed description as after.
Embodiment
With reference to embodiment, the embodiment to the present invention is described in further detail.Following examples are used for
Illustrate the present invention, but be not limited to the scope of the present invention.
Embodiment 1
A kind of processing method of silicon chip of solar cell is present embodiments provided, specific method is as follows
(1) surface chemistry corrosion treatment is carried out to polysilicon chip using potassium hydroxide (KOH) aqueous solution, to remove monocrystalline silicon
The damage layer on surface, processing time is 200s, and treatment temperature is 80 DEG C, wherein, the concentration of the KOH aqueous solution is 2%.
(2) silicon chip after step (1) processing is subjected to borehole processing 50s at 30 DEG C after washing, made during borehole processing
The first treatment fluid is used, wherein containing HF, H2O2, silver ion, the first additive and water, wherein, HF concentration is 5%, H2O2Concentration is
10%, the concentration of silver ion is 1 × 10-6Mol/L, the concentration 5ppm of the first additive.
(3) by the silicon chip after step (2) processing after washing, de- wash at noble metal is carried out at 30 DEG C with second processing liquid
Reason, processing time is 60s, and wherein second processing liquid includes ammoniacal liquor and water, and the wherein concentration of ammoniacal liquor is 8%.
(4) silicon chip after step (3) processing is subjected to expanding treatment at 40 DEG C after washing, processing time is 100s,
The 3rd treatment fluid is used during processing, wherein containing HF, HNO3, with acrylic copolymer, fluorin modified crylic acid copolymer, poly- diformazan
The Second addition and water of base oxosilane, polyether-modified poly dimethyl oxosilane composition.Wherein HF concentration is 5%, HNO3Concentration
For 20%, the concentration of Second addition is 1%.
(5) silicon chip after step (4) processing is immersed into fourth process liquid after washing and carries out moditied processing, located at 30 DEG C
Manage the 3rd constituted in 20s, fourth process liquid containing KOH, with glucose, 18- crown ethers -6, butyl glycol ether, propylene glycol propyl ether
The concentration of additive and water, wherein KOH is 2%, and the concentration of the 3rd additive is 1%.
(6) by the silicon chip after step (5) processing after washing in HCl and H2O2The aqueous solution in carry out pickling processes, 60
200s is handled at DEG C, wherein HCl concentration is 3%, H2O2Concentration be 2%.
(7) silicon chip after step (6) processing is subjected to pickling processes again in the HF aqueous solution after washing, at 20 DEG C
Lower processing 200s, wherein HF concentration are 10%.
(8) the silicon chip after step (7) processing is completed into the black silicon treatment process of wet method of monocrystalline silicon through washing, drying.
Embodiment 2
A kind of processing method of silicon chip of solar cell is present embodiments provided, specific method is as follows：
(1) surface chemistry corrosion treatment is carried out to monocrystalline silicon piece using the KOH aqueous solution, to remove the damage of monocrystalline silicon surface
Layer, processing time is 200s, and treatment temperature is 80 DEG C, wherein, the concentration of the KOH aqueous solution is 5%.
(2) silicon chip after step (1) processing is subjected to borehole processing 180s at 30 DEG C after washing, made during borehole processing
The first treatment fluid is used, wherein containing HF, H2O2, silver ion, with polyacrylic acid, PDLLA, fluorocarbon surfactant composition
First additive and water, wherein, HF concentration is 5%, H2O2Concentration is 5%, and the concentration of silver ion is 1 × 10-6Mol/L, first
The concentration 6ppm of additive.
(3) by the silicon chip after step (2) processing after washing, de- wash at noble metal is carried out at 30 DEG C with second processing liquid
Reason, processing time is 50s, and wherein second processing liquid includes ammoniacal liquor and water, and the concentration of ammoniacal liquor is 10%.
(4) silicon chip after step (3) processing is subjected to expanding treatment at 40 DEG C after washing, processing time is 120s,
The 3rd treatment fluid is used during processing, wherein containing HF, HNO3, with acrylic copolymer, fluorin modified crylic acid copolymer, poly- diformazan
The Second addition and water of base oxosilane, polyether-modified poly dimethyl oxosilane composition.Wherein HF concentration is 5%, HNO3Concentration
For 15%, Second addition concentration is 1%.
(5) silicon chip after step (4) processing is immersed into fourth process liquid after washing and carries out moditied processing, located at 30 DEG C
Manage the 3rd constituted in 20s, fourth process liquid containing KOH, with glucose, 18- crown ethers -6, butyl glycol ether, propylene glycol propyl ether
The concentration of additive and water, wherein KOH is 3%, and the concentration of the 3rd additive is 1%.
(6) by the silicon chip after step (5) processing after washing in HCl and H2O2The aqueous solution in carry out pickling processes, 60
200s is handled at DEG C, wherein HCl concentration is 3%, H2O2Concentration be 2%.
(7) silicon chip after step (6) processing is subjected to pickling processes again in the HF aqueous solution after washing, at 20 DEG C
Lower processing 200s, wherein HF concentration are 10%.
(8) the silicon chip after step (7) processing is completed into the black silicon treatment process of wet method of monocrystalline silicon through washing, drying.
Embodiment 3
Polysilicon chip is handled as control experiment using the sour making herbs into wool of conventional polycrystalline, comprised the following steps that：
(1) water is cleaned；
(2) sour making herbs into wool, uses HF and HNO3System, coordinates certain additive (such as polycrystalline flocking additive)；
(3) water is rinsed；
(4) porous silicon is removed using KOH；
(5) water is rinsed；
(6) HF removes removing oxide layer；
(7) wash, dry up, complete whole flow process.
Embodiment 4
Monocrystalline silicon piece is handled as control experiment using the making herbs into wool of conventional single alkali, specific method is as follows：
(1) prerinse：Use KOH and H2O2System；
(2) alkali making herbs into wool is carried out after washing, using KOH, coordinates certain additive (such as monocrystalline flocking additive)；
(3) KOH and H is used after washing2O2Cleaned；
(4) metal ion and oxide layer are removed using HCl and HF after washing；
(5) wash, dry up, complete whole flow process.
Using the technique in above-described embodiment 1-4, after simple subsequent treatment, in AM1.5, light intensity 1000W, 25 DEG C of temperature
Under the conditions of measure its unit for electrical property parameters, as a result as shown in Table 1 and Table 2.
The unit for electrical property parameters of polysilicon under the different disposal technique of table 1
| Silicon chip | Uoc | Isc | FF | Rs | Rsh | EFF |
| Embodiment 1 | 0.6332 | 8.900 | 80.39 | 1.88 | 1054 | 18.62% |
| Embodiment 3 | 0.6354 | 9.085 | 80.48 | 1.56 | 1107 | 19.09% |
Wherein, the Voc in table 1 represents open-circuit voltage, and Isc represents short circuit current flow, and FF represents fill factor, curve factor, and Rs represents series connection
Resistance, Rsh represents parallel resistance, and EFF represents conversion efficiency.
The unit for electrical property parameters of the different disposal technique lower mono-crystalline silicon of table 2
| Silicon chip | Uoc | Isc | FF | Rs | Rsh | EFF |
| Embodiment 2 | 0.6421 | 9.460 | 80.66 | 2.00 | 896 | 20.06% |
| Embodiment 4 | 0.6452 | 9.533 | 80.92 | 2.00 | 910 | 20.38% |
Wherein, the Voc in table 2 represents open-circuit voltage, and Isc represents short circuit current flow, and FF represents fill factor, curve factor, and Rs represents series connection
Resistance, Rsh represents parallel resistance, and EFF represents conversion efficiency.
As can be seen from Table 1 and Table 2, using the monocrystalline silicon and polysilicon handled by the method for the present invention, its electrical property
Parameter is superior to improve than embodiment 3 as the embodiment 3 and embodiment 4 of control, the wherein photoelectric transformation efficiency of embodiment 1
0.47%, the photoelectric transformation efficiency of embodiment 2 improves 0.32% than embodiment 4, and this is very big in area of solar cell
Improve.It can be seen that, the electrical property of silicon materials can be significantly improved using the black silicon technology of wet method of the present invention, the crystal silicon sun is effectively increased
The photoelectric transformation efficiency of energy battery.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of processing method of silicon chip of solar cell, it is characterised in that comprise the following steps：
(1) chemical attack processing is carried out to silicon chip surface at 40-90 DEG C using aqueous slkali, to remove the damage of the silicon chip surface
Hinder layer；
(2) silicon chip after step (1) processing is immersed into progress borehole processing in the first treatment fluid at 5-40 DEG C, then in 10-
Immerse in second processing liquid take off at 40 DEG C and wash noble metal processing, wherein, first treatment fluid includes hydrofluoric acid, peroxidating
Hydrogen, precious metal ion and water, the second processing liquid include ammoniacal liquor and water；
(3) immersed after the silicon chip washing treated step (2) at 20-40 DEG C in the 3rd treatment fluid and carry out expanding treatment, institute
Stating the 3rd treatment fluid includes hydrofluoric acid, nitric acid and water；
(4) moditied processing, the fourth process liquid will be carried out in immersion fourth process liquid after the silicon chip washing after step (3) processing
Including alkali and water；
(5) hydrochloric acid is immersed at 40-90 DEG C after the silicon chip washing treated step (4) and the mixing of aqueous hydrogen peroxide solution is molten
To remove residual metal ions in liquid, wash, then immersed at 20-40 DEG C in the aqueous solution of hydrofluoric acid with except oxide layer,
Washing, drying.
2. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：It is described in step (1)
The crystal formation of silicon chip is monocrystalline, polycrystalline or class monocrystalline.
3. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：In step (1), alkali is
One or more in sodium hydroxide, potassium hydroxide and TMAH.
4. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：It is described in step (2)
Precious metal ion is the one or more in gold ion, silver ion, platinum ion and palladium ion.
5. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：It is described in step (2)
First treatment fluid also includes the first additive, and first additive is polyacrylic acid, poly- D, Pfansteihl, polyvinyl alcohol and fluorine carbon
One or more in surfactant.
6. the processing method of silicon chip of solar cell according to claim 1 or 5, it is characterised in that：In step (2),
The mass fraction of hydrofluoric acid is 5-20% in first treatment fluid, and the mass fraction of hydrogen peroxide is 0.1-10%.
7. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：It is described in step (3)
3rd treatment fluid also includes Second addition, and the Second addition is polyvinyl alcohol, triethanolamine, tartaric acid, silane coupled
In agent, acrylic copolymer, fluorin modified crylic acid copolymer, poly dimethyl oxosilane and polyether-modified poly dimethyl oxosilane
It is one or more of.
8. the processing method of the silicon chip of solar cell according to claim 1 or 7, it is characterised in that：In step (3),
The mass fraction of hydrofluoric acid is 1-10% in 3rd treatment fluid, and the mass fraction of nitric acid is 10-40%.
9. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：It is described in step (4)
Fourth process liquid also includes the 3rd additive, and the 3rd additive is vinyl acetate, glucose, acrylic copolymer, 18- hats
Ether -6,15- crown ethers -5,12- crown ethers -4, butyl glycol ether, butyl, propylene glycol propyl ether, propylene glycol monomethyl ether, propane diols
One or more in butyl ether, dipropylene glycol propyl ether and tripropylene glycol methyl ether.
10. the processing method of silicon chip of solar cell according to claim 1, it is characterised in that：In step (5), mix
The mass fraction for closing hydrochloric acid in solution is 3-7%, and the mass fraction of hydrogen peroxide is 2-5%.
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| CN107868983A (en) * | 2017-10-19 | 2018-04-03 | 维科诚（苏州）光伏科技有限公司 | A kind of etching method of Buddha's warrior attendant wire cutting polysilicon chip |
| CN108130599A (en) * | 2017-10-19 | 2018-06-08 | 维科诚（苏州）光伏科技有限公司 | A kind of pre- etching method of Buddha's warrior attendant wire cutting polysilicon chip |
| CN108172662A (en) * | 2017-12-26 | 2018-06-15 | 苏州日弈新电子科技有限公司 | A kind of processing method of solar black silicon cell silicon wafer |
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