CN105040108B - The etching method of polysilicon solar cell - Google Patents
The etching method of polysilicon solar cell Download PDFInfo
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- CN105040108B CN105040108B CN201510518472.0A CN201510518472A CN105040108B CN 105040108 B CN105040108 B CN 105040108B CN 201510518472 A CN201510518472 A CN 201510518472A CN 105040108 B CN105040108 B CN 105040108B
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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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- Y02E10/00—Energy generation through renewable energy sources
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Abstract
A kind of etching method of polysilicon solar cell, the making herbs into wool aqueous solution include：Hydrofluoric acid 5 20%, nitric acid 25 55%, silicofluoric acid 0.5 5%, acetic acid 0.1 0.5%, additive 0.5 1.5%, excess water；Additive is：Polyvinyl alcohol 0.2 0.8%, triethanolamine 0.1 6%, HPMA 1 6%, polyvinylpyrrolidone 0.05 0.1%, excess water：0 30 DEG C of making herbs into wool aqueous temperature, silicon chip is placed in 100 300s in the aqueous solution, and carries out ultrasonic vibration simultaneously, the 60KHZ of supersonic frequency 40；Taking-up, which is placed in the cleaning fluid of sodium hydroxide 0.2 0.5%, neopelex 0.5 2%, is cleaned, takes out drying.Good with stability, temperature is easily controllable, and polysilicon surface falls into the advantages of light effect is good and the optoelectronic transformation efficiency of battery is high, and matte is uniform, reflectivity is low.
Description
Technical field
The present invention relates to preparation method of solar battery technical field, and in particular to a kind of system of polysilicon solar cell
Velvet figures method.
Background technology
Polysilicon be melting elemental silicon when being solidified under the conditions of supercooling, silicon atom with diamond lattice morphologic arrangement into permitted
More nucleus, as these nucleus grow up to the different crystal grain of high preferred orientation, then these crystal grain combine, and just crystallize into polysilicon.It is more
Crystal silicon is different due to the crystal orientation of each crystal grain, it is impossible to caustic corrosion is used as monocrystalline silicon；In order to obtain good polysilicon
Matte, there are a variety of methods, such as reactive ion etching method, mechanical carving groove method and chemical corrosion method at present.Wherein chemical corrosion method,
Due to easy to operate, repeated strong, large-scale application has been obtained in industrialized production.Its principle is as follows：It is main to use acid
Process for etching, system mainly include nitric acid and hydrofluoric acid, and specific reaction equation is as follows：
3Si+4HNO3——3SiO2+2H2O+4NO
SiO2+6HF——H2(SiF6)+2H2O
Wherein silicon is supported into fine and close silica not soluble in water and is attached to silicon chip table by nitric acid as strong oxidant
Face, the further reaction of nitric acid and silicon is prevented, but silica can react with the hydrofluoric acid in solution, and production dissolves in
The complex compound H2 (SiF6) of water, causes silica to destroy, now nitric acid chemically reacts again with silicon, and silicon chip surface is continuous
Be corroded, ultimately form " worm channel shape " structure of continuous densification.Although this method does not need specific consersion unit, technique
Relatively easy, manufacturing cost is low, but the method is due to being pure chemistry reaction, acid in silicon chip reaction speed is fast, stability is not allowed
Easy to control, temperature of reaction etc. is also to influence the key factor of silicon wafer wool making effect, and somewhat controlling bad can cause polysilicon table
The deficiencies of face falls into light effect and the optoelectronic transformation efficiency of battery is low, and battery pile face is uneven, reflectivity is high.
The content of the invention
The present invention is directed to the above-mentioned deficiency of prior art, there is provided a kind of stability is good, and temperature is easily controllable, polysilicon surface
Sunken light effect is good and the optoelectronic transformation efficiency of battery is high, the etching method for the polysilicon solar cell that matte is uniform, reflectivity is low.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of system of polysilicon solar cell
Velvet figures method, step include：
(1) the making herbs into wool aqueous solution is prepared first in texturing slot, preparation raw material includes：Hydrofluoric acid 5-20wt%, nitric acid 25-
55wt%, silicofluoric acid 0.5-5wt%, acetic acid 0.1-0.5wt%, additive 0.5-1.5wt%, surplus are water；By above-mentioned each group
Divide and be mixed and stirred for uniformly；
Described additive forms：Polyvinyl alcohol 0.2-0.8wt%, triethanolamine 0.1-6wt%, hydrolyzed polymaleic anhydride
Acid anhydride 1-6wt%, polyvinylpyrrolidone 0.05-0.1wt%, surplus are water：
(2) it is 0-30 DEG C the making herbs into wool aqueous solution of step (1) to be maintained into temperature, and polysilicon chip then is placed in into the above-mentioned aqueous solution
Middle placement 100-300s, and ultrasonic vibration is carried out simultaneously, supersonic frequency 40-60KHZ；Then take out and be placed in sodium hydroxide 0.2-
0.5wt%, neopelex 0.5-2wt%, surplus are to be cleaned in the cleaning fluid that water is formed, take out drying i.e.
Can.
Preferably, preparing the making herbs into wool aqueous solution in described texturing slot, preparation raw material includes：Hydrofluoric acid 10-15wt%, nitre
Sour 25-45wt%, silicofluoric acid 0.5-1.5wt%, acetic acid 0.1-0.2wt%, additive 0.5-1.0wt%, surplus are water.
Preferably, described additive composition is：Polyvinyl alcohol 0.2-0.5%, triethanolamine 0.1-0.8%, hydrolysis
HPMA 1-2%, polyvinylpyrrolidone 0.05-0.08%, surplus are water.
Advantages of the present invention and excellent effect：
1. the above-mentioned preparation process of the present invention, silicofluoric acid, vinegar are with the addition of in traditional hydrofluoric acid, nitric acid making herbs into wool liquid
Acid, the two can play a part of corrosion inhibiter, fast erosion of the hydrofluoric acid to polycrystalline surface be reduced, so as to increase making herbs into wool liquid
Stability and controllability；The addition of particularly acetic acid reduces overall mixed liquid concentration, so as to reduce corrosion rate, subtracts simultaneously
The small surface tension of polysilicon chip, depart from beneficial to the bubble for being attached to polysilicon surface, so that making herbs into wool liquid and polycrystalline
Silicon chip surface fully, uniformly contacts, and improves making herbs into wool effect and the uniformity.In addition, making herbs into wool process uses ultrasonic vibration, can also
Realize that the bubble that making herbs into wool process is attached to polysilicon surface departs from, prevent the masking to surface, realize that each corner is uniformly rotten
Erosion, prepares preferable matte.In addition, the present invention also with the addition of additive in suede liquid so that the matte rule of preparation, reflection
Rate is low, and course of reaction is controllable.
2. the cleaning fluid after the making herbs into wool of the present invention, which has, can effectively go the removal of impurity, uniformity is good after surface clean, reflectivity
The advantages of low.
Brief description of the drawings
Silicon wafer wool making microgram prepared by Fig. 1 embodiment of the present invention 1.
Silicon wafer wool making microgram prepared by Fig. 2 embodiment of the present invention 2.
Embodiment
The present invention is further described in detail with reference to embodiments, but is not limited to this.
The silicon chip that embodiment uses is commercially available polysilicon silicon chip, and size is 2 × 2cm, thickness 180-200 microns, resistivity
For 0.5-1.5 Ω cm.
Embodiment 1
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of system of polysilicon solar cell
Velvet figures method, step include：
(1) the making herbs into wool aqueous solution is prepared first in texturing slot, preparation raw material includes：Hydrofluoric acid 5wt%, nitric acid 25wt%,
Silicofluoric acid 0.5wt%, acetic acid 0.1wt%, additive 0.5wt%, surplus are water；Above-mentioned each component is mixed and stirred for uniformly；
Described additive forms：Polyvinyl alcohol 0.5%, triethanolamine 0.2%, HPMA 3%, poly- second
Alkene pyrrolidone 0.06%, surplus are water：
(2) it is 15 DEG C the making herbs into wool aqueous solution of step (1) to be maintained into temperature, and then polysilicon chip is placed in the above-mentioned aqueous solution
120s is placed, and carries out ultrasonic vibration simultaneously, supersonic frequency 40KHZ；Then take out and be placed in sodium hydroxide 0.3%, dodecyl
Benzene sulfonic acid sodium salt 0.8%, surplus are to be cleaned in the cleaning fluid that water is formed, take out drying.
Shown in Fig. 1, matte prepared by the embodiment of the present invention, matte size uniform is tiny and than more uniform.
Embodiment 2
With embodiment 1, difference is other steps：The making herbs into wool aqueous solution is prepared in described texturing slot, preparation raw material includes：
Hydrofluoric acid 10wt%, nitric acid 45wt%, silicofluoric acid 1.5wt%, acetic acid 0.2wt%, additive 1.0wt%, surplus are water.
Described additive forms：Polyvinyl alcohol 0.5%, triethanolamine 0.7%, HPMA 1.5%, gather
Vinylpyrrolidone 0.07%, surplus are water.
Shown in Fig. 2, matte prepared by the embodiment of the present invention, matte size uniform is tiny and than more uniform.
Comparative example
(1) the making herbs into wool aqueous solution is prepared first in texturing slot, preparation raw material includes：Hydrofluoric acid 5wt%, nitric acid 25wt%,
Silicofluoric acid 0.5wt%, additive 0.5wt%, surplus are water；Above-mentioned each component is mixed and stirred for uniformly；
Described additive forms：Polyvinyl alcohol 0.5%, triethanolamine 0.2%, HPMA 3%, poly- second
Alkene pyrrolidone 0.06%, surplus are water：
(2) it is 15 DEG C the making herbs into wool aqueous solution of step (1) to be maintained into temperature, and then polysilicon chip is placed in the above-mentioned aqueous solution
120s is placed, and carries out ultrasonic vibration simultaneously, supersonic frequency 40KHZ；Then take out and be placed in sodium hydroxide 0.3%, dodecyl
Benzene sulfonic acid sodium salt 0.8%, surplus are to be cleaned in the cleaning fluid that water is formed, take out drying.
The product prepared by micro- sem observation, comparative example, its matte is uneven, with the restricted differences of above-described embodiment 1-2
Not.
Shown in Fig. 1, matte prepared by the embodiment of the present invention, matte size uniform is tiny and than more uniform.
Battery performance parameter prepared by 1-2 of the embodiment of the present invention and comparative example is shown in Table 2：
Battery performance parameter prepared by the embodiment 1-2 of table 2 and comparative example
It was found from above-mentioned parameter, battery prepared by method of the invention has that reflectivity is low, can effectively improve battery conversion
The advantages of efficiency.
Claims (3)
1. a kind of etching method of polysilicon solar cell, it is characterised in that step includes：
(1) the making herbs into wool aqueous solution is prepared first in texturing slot, preparation raw material includes：Hydrofluoric acid 5-20wt%, nitric acid 25-
55wt%, silicofluoric acid 0.5-5wt%, acetic acid 0.1-0.5wt%, additive 0.5-1.5wt%, surplus are water；By above-mentioned each group
Divide and be mixed and stirred for uniformly；
Described additive forms：Polyvinyl alcohol 0.2-0.8wt%, triethanolamine 0.1-6wt%, HPMA 1-
6wt%, polyvinylpyrrolidone 0.05-0.1wt%, surplus are water：
(2) it is 0-30 DEG C the making herbs into wool aqueous solution of step (1) to be maintained into temperature, and then polysilicon chip is placed in the above-mentioned aqueous solution and put
100-300s is put, and carries out ultrasonic vibration simultaneously, supersonic frequency 40-60KHZ；Then take out and be placed in sodium hydroxide 0.2-
0.5wt%, neopelex 0.5-2wt%, surplus are to be cleaned in the cleaning fluid that water is formed, take out drying i.e.
Can.
2. the etching method of polysilicon solar cell according to claim 1, it is characterised in that in described texturing slot
The making herbs into wool aqueous solution is prepared, preparation raw material includes：Hydrofluoric acid 10-15wt%, nitric acid 25-45wt%, silicofluoric acid 0.5-1.5wt%,
Acetic acid 0.1-0.2wt%, additive 0.5-1.0wt%, surplus are water.
3. the etching method of polysilicon solar cell according to claim 1, it is characterised in that described additive group
Turn into：Polyvinyl alcohol 0.2-0.5wt%, triethanolamine 0.1-0.8wt%, HPMA 1-2wt%, polyvinyl pyrrole
Alkanone 0.05-0.08wt%, surplus are water.
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| CN106098810B (en) * | 2016-06-27 | 2018-11-13 | 苏州阿特斯阳光电力科技有限公司 | A kind of preparation method of crystal silicon solar energy battery suede structure |
| CN106119976B (en) * | 2016-08-19 | 2018-08-14 | 常州时创能源科技有限公司 | Additive and its application of the black silicon making herbs into wool of polycrystalline with reaming acid solution |
| CN106222755A (en) * | 2016-09-30 | 2016-12-14 | 杭州飞鹿新能源科技有限公司 | Additive and application process thereof for polycrystalline silicon texturing |
| CN109119337A (en) * | 2017-06-23 | 2019-01-01 | 镇江仁德新能源科技有限公司 | A kind of solar-grade polysilicon piece surface wool manufacturing method |
| CN108004597A (en) * | 2017-11-09 | 2018-05-08 | 润峰电力有限公司 | A kind of polysilicon flocking additive and its etching method |
| CN108470795A (en) * | 2018-02-12 | 2018-08-31 | 镇江仁德新能源科技有限公司 | A kind of solar-grade polysilicon piece surface wool manufacturing method |
| CN108766866A (en) * | 2018-05-25 | 2018-11-06 | 南京八度阳光太阳能科技有限公司 | A kind of fluff making device used for solar batteries |
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