CN107623055B - A kind of preparation method of quasi- monocrystalline battery - Google Patents
A kind of preparation method of quasi- monocrystalline battery Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of quasi- monocrystalline battery, include the following steps: quasi-monocrystalline silicon impregnating the first preset time in the first mixed liquor of the first preset temperature, wherein the first mixed liquor includes hydrofluoric acid and hydrogen peroxide；The second mixed liquor is added into the first mixed liquor to obtain neutral mixed liquor, and quasi-monocrystalline silicon is cleaned into the second preset time in neutral mixed liquor, wherein the second mixed liquor includes potassium hydroxide and ammonium hydroxide；By the quasi-monocrystalline silicon after prerinse in the third mixed liquor of the second preset temperature pickling third preset time；Quasi-monocrystalline silicon after pickling is successively carried out to chemical reaction etching and physical ion bombardment processing；Quasi- monocrystalline battery will be obtained after treated quasi-monocrystalline silicon successively carries out boron diffusion, phosphorus diffusion, plated film and the processing of printing electrode of the black silicon of dry method.The quasi- monocrystalline battery that the present invention is prepared, the sunken light effect of flannelette is preferable, and battery conversion efficiency is higher, improves battery quality.
Description
Technical field
The present invention relates to solar cell preparation technology, in particular to a kind of preparation method of quasi- monocrystalline battery.
Background technique
In recent years, gradually in short supply with fuel source, solar battery as a kind of new energy utilization mode, due to
It has many advantages, such as cleaning and it is renewable, gradually obtained being more and more widely used research.
In the fabrication of a solar cell, N-type quasi-monocrystalline silicon is also a kind of relatively conventional silicon wafer raw material.N-type
Quasi- monocrystalline refers to a kind of a kind of novel crystal structure grown on the basis of single crystal seed by directional solidification mode, product
Matter is between monocrystalline and polycrystalline.Specifically, N-type quasi-monocrystalline silicon doped chemical is phosphorus, the solar battery tool produced
There are the multinomial advantages such as low light attenuation, high minority carrier life time, high conversion efficiency and high generated energy.At the same time, raw by ingot ways
The N-type quasi- monocrystalline that output is come, silicon area (24571mm2) it compared to fillet N-type monocrystalline (is 210mm, area with diameter
24431mm2For) area for be higher by 0.56%, it is corresponding to promote about 0.12% if being converted to solar energy efficiency,
Therefore N-type quasi- monocrystalline will have biggish market development potential.
However, in the preparation process of existing solar battery, due to using traditional alkali making herbs into wool skill to quasi-monocrystalline silicon
Art, silicon chip surface can generate more speck, and the speck of generation can more reflect away sunlight to reduce the sun
The transfer efficiency of energy.
Summary of the invention
Based on this, it is an object of the invention to propose a kind of solar energy that can improve quasi- monocrystalline battery to a certain extent
The preparation method of the quasi- monocrystalline battery of transfer efficiency, to meet practical application request.
The present invention proposes a kind of preparation method of quasi- monocrystalline battery, for preparing the quasi- monocrystalline based on a quasi-monocrystalline silicon
Battery, wherein the described method includes:
The black silicon making herbs into wool of wet process: the quasi-monocrystalline silicon is impregnated to first in the first mixed liquor of the first preset temperature and is preset
Time, wherein first mixed liquor includes hydrofluoric acid and hydrogen peroxide；
Prerinse: the second mixed liquor is added in the first mixed liquor of Xiang Suoshu to obtain neutral mixed liquor, and will be described quasi- single
Crystal silicon chip cleans the second preset time in the neutral mixed liquor, wherein second mixed liquor includes potassium hydroxide and hydrogen
Amine-oxides；
Pickling: by the quasi-monocrystalline silicon after prerinse, pickling third is pre- in the third mixed liquor of the second preset temperature
If the time, wherein the third mixed liquor includes hydrofluoric acid and hydrochloric acid；
Dry method black silicon processing: the quasi-monocrystalline silicon after pickling is successively carried out chemical reaction etching and physics from
Sub- bombardment processing；
The preparation of quasi- monocrystalline battery: by treated the quasi-monocrystalline silicon successively the carries out boron diffusion of the black silicon of dry method, phosphorus diffusion,
The quasi- monocrystalline battery is obtained after plated film and processing of printing electrode.
The preparation method of quasi- monocrystalline battery proposed by the present invention, first by a quasi-monocrystalline silicon after the black silicon making herbs into wool of wet process,
Prerinse, pickling are successively carried out again, then carries out dry method black silicon processing again, finally by the black silicon of dry method treated quasi-monocrystalline silicon
Corresponding quasi- monocrystalline battery is obtained after successively carrying out boron diffusion, phosphorus diffusion, plated film and processing of printing electrode.Due to black through wet process
There is silicon making herbs into wool and the black silicon of dry method treated quasi-monocrystalline silicon good flannelette to fall into light effect, therefore can be largely
The upper solar energy conversion efficiency for improving the quasi- monocrystalline battery, provides the total quality of product, meets application demand.
The preparation method of the quasi- monocrystalline battery, wherein carrying out the step of chemical reaction etches includes:
The quasi-monocrystalline silicon that will be obtained after pickling is reacted in the atmosphere of SF6 to obtain SiF4 gas；
Occur after passivation reaction obtains the first passivation product between the SiF4 gas and the quasi-monocrystalline silicon, described the
In one passivation product deposition to the quasi-monocrystalline silicon.
The preparation method of the quasi- monocrystalline battery, wherein carrying out the step of physical ion bombardment is handled includes:
Using the energetic ion under DC pulse bias effect, first passivation hit in the quasi-monocrystalline silicon is produced
Object is to form the first flannelette.
The preparation method of the quasi- monocrystalline battery, wherein described by the black silicon of dry method treated the quasi-monocrystalline silicon
After the step of carrying out boron diffusion, the method also includes:
Single side etching is carried out to the quasi-monocrystalline silicon after the boron DIFFUSION TREATMENT；
The Pyrex on the quasi-monocrystalline silicon surface are removed in HF atmosphere, and by polyethylene film to institute
It states quasi-monocrystalline silicon and carries out overlay film.
The preparation method of the quasi- monocrystalline battery, wherein after the step of quasi-monocrystalline silicon is carried out phosphorus diffusion,
The method also includes:
The phosphorosilicate glass on the quasi-monocrystalline silicon surface is removed in HF atmosphere.
The preparation method of the quasi- monocrystalline battery, wherein include: to the step of quasi-monocrystalline silicon progress plated film
After the front of the quasi-monocrystalline silicon plates one layer of pellumina, in the front and back sides of the quasi-monocrystalline silicon point
Layer of sin film is not plated.
The preparation method of the quasi- monocrystalline battery, wherein print electrode described to described in quasi-monocrystalline silicon progress
The step of after, the method also includes:
It is 200~300 DEG C in temperature, electric current carries out the surface of the quasi- monocrystalline battery in the environment of being 16~18A scarce
Fall into Passivation Treatment.
The preparation method of the quasi- monocrystalline battery, wherein the black silicon making herbs into wool of wet process is being carried out to the quasi-monocrystalline silicon
The step of before, the method also includes:
The quasi-monocrystalline silicon is impregnated into 2min in 6~8 DEG C of prefabricated pickling solution, the prefabricated pickling solution includes volume
Than the hydrofluoric acid and nitric acid for 1:6.
The preparation method of the quasi- monocrystalline battery, wherein the temperature range of first preset temperature is 25 DEG C -30 DEG C,
First preset time is 5~6min.
The preparation method of the quasi- monocrystalline battery, wherein second preset time is 1~3min, and described second is default
Temperature is 20 DEG C, and the third preset time is 1min.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the functional block diagram of the preparation method of quasi- monocrystalline battery in first embodiment of the invention；
Fig. 2 is the flow chart of the preparation method of quasi- monocrystalline battery in second embodiment of the invention.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing
Give preferred embodiment of the invention.But the invention can be realized in many different forms, however it is not limited to this paper institute
The embodiment of description.On the contrary, purpose of providing these embodiments is make it is more thorough and comprehensive to the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the listed item of pass.
Embodiment one
Referring to Fig. 1, for the preparation method of the quasi- monocrystalline battery in first embodiment, for being based on a quasi-monocrystalline silicon
Prepare the quasi- monocrystalline battery, wherein the described method includes:
The quasi-monocrystalline silicon is impregnated the first preset time in the first mixed liquor of the first preset temperature by S101,
Described in the first mixed liquor include hydrofluoric acid and hydrogen peroxide.
A quasi-monocrystalline silicon is chosen first, using hydrofluoric acid and nitric acid, is carried out according to the proportion that volume ratio is 1:6 with obtained
To after mix acid liquor, quasi-monocrystalline silicon is put into the mix acid liquor and carries out processing 2min, to remove the damaging layer on surface.Its
In, the temperature of the mix acid liquor is 6~8 DEG C.
The first mixing after the surface damage layer of removal quasi-monocrystalline silicon, by the quasi-monocrystalline silicon at 25 DEG C -30 DEG C
5~6min is impregnated in liquid.Wherein, which is the mixing liquid comprising hydrofluoric acid and hydrogen peroxide.Wherein, the processing side
Method is the black silicon making herbs into wool of wet process, primarily to the quasi-monocrystalline silicon surface to be formed to the etch pit of multiple circular holes.
The second mixed liquor is added in the first mixed liquor of S102, Xiang Suoshu to obtain neutral mixed liquor, and by the quasi- monocrystalline
Silicon wafer cleans the second preset time in the neutral mixed liquor, wherein second mixed liquor includes potassium hydroxide and hydrogen-oxygen
Change ammonium.
After carrying out the black silicon making herbs into wool processing of above-mentioned wet process, to above-mentioned acidity the first mixed liquor (including hydrofluoric acid with pair
Oxygen water) in potassium hydroxide and ammonium hydroxide is added to neutralize former first mixed liquor, to obtain neutral mixed liquor.Then
The quasi-monocrystalline silicon obtained after the black silicon making herbs into wool of wet process is cleaned into 1~3min in the neutrality mixed liquor.Wherein, the washing and cleaning operation
Mainly silicon hole (etch pit) is cleaned.
S103, by the quasi-monocrystalline silicon after prerinse, pickling third is pre- in the third mixed liquor of the second preset temperature
If the time, wherein the third mixed liquor includes hydrofluoric acid and hydrochloric acid.
After the silicon hole that alignment monocrystalline silicon sheet surface generates carries out prerinse operation, by the quasi-monocrystalline silicon at 20 DEG C
Pickling 1min in the mix acid liquor of hydrofluoric acid and hydrochloric acid.Wherein in the third mixed liquor, hydrofluoric acid volume ratio corresponding with hydrochloric acid
For 1:2.Making herbs into wool face is cleaned using hydrofluoric acid and mixed liquor made of hydrochloric acid, wherein hydrochloric acid is mainly used for neutralizing upper one
Remaining lye is walked, hydrofluoric acid is mainly used for removing the silica on surface, prepare for subsequent cleaning technology.
S104 successively carries out the quasi-monocrystalline silicon after pickling at chemical reaction etching and physical ion bombardment
Reason.
Specifically, when carrying out chemical reaction etching, the quasi-monocrystalline silicon that will be obtained after pickling, in SF6Gas
It is reacted in atmosphere, generates group containing F* and generate volatile SiF in the environment of silicon substrate4(this step is to carve to gas
Erosion effect)；Then O* group and SiF4Gas reaction generates the first passivation product SixOyFz, a passivation product of generation
SixOyFz is deposited to quasi-monocrystalline silicon, so that the continuation of F* group be prevented to be reacted with the silicon wafer on surface.
After carrying out chemical reaction etching, using the energetic ion under DC pulse bias effect, hit described quasi- single
The first passivation product SixOyFz in crystal silicon chip makes F* group continue to carry out with the silicon wafer on surface to form the first flannelette
Reaction, silicon chip surface form the suede structure of random distribution.
S105, by the black silicon of dry method, treated that the quasi-monocrystalline silicon successively carries out boron diffusion, phosphorus diffusion, plated film and print
The quasi- monocrystalline battery is obtained after brush electrode processing.
As described above, quasi-monocrystalline silicon is carried out after carrying out chemical reaction etching and physical ion bombardment processing
Boron DIFFUSION TREATMENT (wherein, the diffusion junction depth of boron diffusion is 0.6-0.7um), carries out single side etching, then after boron DIFFUSION TREATMENT
The Pyrex on quasi-monocrystalline silicon surface are removed in HF atmosphere, and by polyethylene film (PE) to the quasi-monocrystalline silicon
Piece carries out overlay film.
Exposure mask is being carried out to quasi-monocrystalline silicon using polyethylene film (PE) and then is carrying out phosphorus diffusion (wherein, phosphorus diffusion
Junction depth is 0.30-0.35um) processing, the phosphorosilicate glass on quasi-monocrystalline silicon surface is removed in HF atmosphere.Then, at this
Successively plate pellumina and SiN film (wherein, pellumina with a thickness of 15-20nm), back side plating in the front of quasi-monocrystalline silicon
After upper SiN film, it is two-sided print electrode respectively after carry out surface defect Passivation Treatment.Specifically, carrying out at defect passivation
It is 200~300 DEG C in temperature when reason, electric current carries out defect passivation to the surface of the quasi- monocrystalline battery in the environment of being 16~18A
Processing finally obtains quasi- monocrystalline battery.
The preparation method of quasi- monocrystalline battery proposed by the present invention, first by a quasi-monocrystalline silicon after the black silicon making herbs into wool of wet process,
Prerinse, pickling are successively carried out again, then carries out dry method black silicon processing again, finally by the black silicon of dry method treated quasi-monocrystalline silicon
Corresponding quasi- monocrystalline battery is obtained after successively carrying out boron diffusion, phosphorus diffusion, plated film and processing of printing electrode.Due to black through wet process
There is silicon making herbs into wool and the black silicon of dry method treated quasi-monocrystalline silicon good flannelette to fall into light effect, therefore can be largely
The upper solar energy conversion efficiency for improving the quasi- monocrystalline battery, provides the total quality of product, meets application demand.
Embodiment two
Referring to Fig. 2, for the preparation method of the quasi- monocrystalline battery in second embodiment, the specific following institute of preparation process
It states:
A quasi-monocrystalline silicon is chosen first, is put into the mix acid liquor of hydrofluoric acid and nitric acid that volume ratio is 1:6 at immersion
2min is managed to remove the damaging layer on surface, wherein the temperature of the mix acid liquor is 6~8 DEG C.
Then, which is impregnated to 5 in 25 DEG C -30 DEG C of hydrofluoric acid and the mixing liquid of hydrogen peroxide~
6min, wherein the volume ratio of hydrofluoric acid and hydrogen peroxide is 1:2.The processing method is the black silicon making herbs into wool of wet process, primarily to should
Quasi-monocrystalline silicon surface forms the etch pit of multiple circular holes.
Further, the potassium hydroxide and Ammonia progress that volume ratio is 1:3 are added in Xiang Suoshu mixed liquor
It neutralizes, to finally obtain neutral mixed liquor.Then the quasi-monocrystalline silicon that will be obtained after the black silicon making herbs into wool of wet process, in the neutrality mixed liquor
1~3min of middle cleaning.Wherein, which mainly cleans silicon hole (etch pit).
Further, after completing prerinse, by the quasi-monocrystalline silicon 20 DEG C of hydrofluoric acid and hydrochloric acid mixing
Pickling 1min in acid solution.Wherein, the volume ratio of hydrofluoric acid and hydrochloric acid is 1:2.Use mixed liquor pair made of hydrofluoric acid and hydrochloric acid
Making herbs into wool face is cleaned, wherein hydrochloric acid is mainly used for neutralizing the remaining lye of previous step, and hydrofluoric acid is mainly used for removing surface
Silica is prepared for subsequent cleaning technology.
Chemical reaction etching is carried out to the quasi-monocrystalline silicon, the quasi-monocrystalline silicon that will be obtained after pickling, in SF6Gas atmosphere
It is reacted in enclosing, generates group containing F* and generate volatile SiF in the environment of silicon substrate4(this step is etching to gas
Effect)；Then O* group and SiF4Gas reaction generates the first passivation product SixOyFz, a passivation product SixOyFz of generation
In deposition to quasi-monocrystalline silicon, so that the continuation of F* group be prevented to be reacted with the silicon wafer on surface.Then, inclined using DC pulse
Energetic ion under pressure effect hits the first passivation product SixOyFz in quasi-monocrystalline silicon to form the first flannelette, makes F* base
Group continues to be reacted with the silicon wafer on surface, and silicon chip surface forms the suede structure of random distribution.
Further, after carrying out chemical reaction etching and physical ion bombardment processing, quasi-monocrystalline silicon is carried out
Boron DIFFUSION TREATMENT (wherein, the diffusion junction depth of boron diffusion is 0.6-0.7um), carries out single side etching, then after boron DIFFUSION TREATMENT
The Pyrex on quasi-monocrystalline silicon surface are removed in HF atmosphere, and by polyethylene film (PE) to the quasi-monocrystalline silicon
Piece carries out overlay film.
Exposure mask is being carried out to quasi-monocrystalline silicon using polyethylene film (PE) and then is carrying out phosphorus diffusion (wherein, phosphorus diffusion
Junction depth is 0.30-0.35um) processing, the phosphorosilicate glass on quasi-monocrystalline silicon surface is removed in HF atmosphere.Then, at this
Successively plate pellumina and SiN film (wherein, pellumina with a thickness of 15-20nm), back side plating in the front of quasi-monocrystalline silicon
After upper SiN film, it is two-sided print electrode respectively after carry out surface defect Passivation Treatment.Specifically, carrying out at defect passivation
It is 200~300 DEG C in temperature when reason, electric current carries out defect passivation to the surface of the quasi- monocrystalline battery in the environment of being 16~18A
Processing finally obtains quasi- monocrystalline battery.Battery sorting test finally is carried out to quasi- monocrystalline battery obtained, is turned with finding out solar energy
Change the highest battery of efficiency.In the present embodiment, the transfer efficiency of solar battery obtained can be up to 21.5%.
Embodiment three
A quasi-monocrystalline silicon is chosen first, is put into the mix acid liquor of hydrofluoric acid and nitric acid that volume ratio is 1:6 at immersion
2min is managed to remove the damaging layer on surface, wherein the temperature of the mix acid liquor is 6 DEG C.
Then, which is impregnated into 5min in 25 DEG C of hydrofluoric acid and the mixing liquid of hydrogen peroxide, wherein hydrogen
The volume ratio of fluoric acid and hydrogen peroxide is 1:2.The processing method is the black silicon making herbs into wool of wet process, primarily to by the quasi-monocrystalline silicon table
Face forms the etch pit of multiple circular holes.
Further, the potassium hydroxide and Ammonia progress that volume ratio is 1:3 are added in Xiang Suoshu mixed liquor
It neutralizes, to finally obtain neutral mixed liquor.Then the quasi-monocrystalline silicon that will be obtained after the black silicon making herbs into wool of wet process, in the neutrality mixed liquor
Middle cleaning 1min.Wherein, which mainly cleans silicon hole (etch pit).
Further, after completing prerinse, by the quasi-monocrystalline silicon 20 DEG C of hydrofluoric acid and hydrochloric acid mixing
Pickling 1min in acid solution.Wherein, the volume ratio of hydrofluoric acid and hydrochloric acid is 1:2.Use mixed liquor pair made of hydrofluoric acid and hydrochloric acid
Making herbs into wool face is cleaned, wherein hydrochloric acid is mainly used for neutralizing the remaining lye of previous step, and hydrofluoric acid is mainly used for removing surface
Silica is prepared for subsequent cleaning technology.
Chemical reaction etching is carried out to the quasi-monocrystalline silicon, the quasi-monocrystalline silicon that will be obtained after pickling, in SF6Gas atmosphere
It is reacted in enclosing, generates group containing F* and generate volatile SiF in the environment of silicon substrate4(this step is etching to gas
Effect)；Then O* group and SiF4Gas reaction generates the first passivation product SixOyFz, a passivation product SixOyFz of generation
In deposition to quasi-monocrystalline silicon, so that the continuation of F* group be prevented to be reacted with the silicon wafer on surface.Then, inclined using DC pulse
Energetic ion under pressure effect hits the first passivation product SixOyFz in quasi-monocrystalline silicon to form the first flannelette, makes F* base
Group continues to be reacted with the silicon wafer on surface, and silicon chip surface forms the suede structure of random distribution.
Further, after carrying out chemical reaction etching and physical ion bombardment processing, quasi-monocrystalline silicon is carried out
Boron DIFFUSION TREATMENT (wherein, the diffusion junction depth of boron diffusion is 0.6um), carries out single side etching, then in HF after boron DIFFUSION TREATMENT
In atmosphere remove quasi-monocrystalline silicon surface on Pyrex, and by polyethylene film (PE) to the quasi-monocrystalline silicon into
Row overlay film.
Exposure mask is being carried out to quasi-monocrystalline silicon using polyethylene film (PE) and then is carrying out phosphorus diffusion (wherein, phosphorus diffusion
Junction depth is 0.30um) processing, the phosphorosilicate glass on quasi-monocrystalline silicon surface is removed in HF atmosphere.Then, single in the standard
Pellumina and SiN film (wherein, pellumina with a thickness of 15nm) is successively plated in the front of crystal silicon chip, and the back side plates SiN film
Later, it is two-sided print electrode respectively after carry out surface defect Passivation Treatment.Specifically, when carrying out defect passivation processing,
Temperature is 200 DEG C, and electric current finally obtains the surface progress defect passivation processing of the quasi- monocrystalline battery in the environment of being 16A quasi- single
Brilliant battery.Battery sorting test finally is carried out to quasi- monocrystalline battery obtained, to find out the highest battery of solar energy conversion efficiency.
In the present embodiment, the transfer efficiency of solar battery obtained can be up to 21.2%.
Example IV
A quasi-monocrystalline silicon is chosen first, is put into the mix acid liquor of hydrofluoric acid and nitric acid that volume ratio is 1:6 at immersion
2min is managed to remove the damaging layer on surface, wherein the temperature of the mix acid liquor is 8 DEG C.
Then, which is impregnated into 6min in 30 DEG C of hydrofluoric acid and the mixing liquid of hydrogen peroxide, wherein hydrogen
The volume ratio of fluoric acid and hydrogen peroxide is 1:2.The processing method is the black silicon making herbs into wool of wet process, primarily to by the quasi-monocrystalline silicon table
Face forms the etch pit of multiple circular holes.
Further, the potassium hydroxide and Ammonia progress that volume ratio is 1:3 are added in Xiang Suoshu mixed liquor
It neutralizes, to finally obtain neutral mixed liquor.Then the quasi-monocrystalline silicon that will be obtained after the black silicon making herbs into wool of wet process, in the neutrality mixed liquor
Middle cleaning 3min.Wherein, which mainly cleans silicon hole (etch pit).
Further, after completing prerinse, by the quasi-monocrystalline silicon 20 DEG C of hydrofluoric acid and hydrochloric acid mixing
Pickling 1min in acid solution.Wherein, the volume ratio of hydrofluoric acid and hydrochloric acid is 1:2.Use mixed liquor pair made of hydrofluoric acid and hydrochloric acid
Making herbs into wool face is cleaned, wherein hydrochloric acid is mainly used for neutralizing the remaining lye of previous step, and hydrofluoric acid is mainly used for removing surface
Silica is prepared for subsequent cleaning technology.
Chemical reaction etching is carried out to the quasi-monocrystalline silicon, the quasi-monocrystalline silicon that will be obtained after pickling, in SF6Gas atmosphere
It is reacted in enclosing, generates group containing F* and generate volatile SiF in the environment of silicon substrate4(this step is etching to gas
Effect)；Then O* group and SiF4Gas reaction generates the first passivation product SixOyFz, a passivation product SixOyFz of generation
In deposition to quasi-monocrystalline silicon, so that the continuation of F* group be prevented to be reacted with the silicon wafer on surface.Then, inclined using DC pulse
Energetic ion under pressure effect hits the first passivation product SixOyFz in quasi-monocrystalline silicon to form the first flannelette, makes F* base
Group continues to be reacted with the silicon wafer on surface, and silicon chip surface forms the suede structure of random distribution.
Further, after carrying out chemical reaction etching and physical ion bombardment processing, quasi-monocrystalline silicon is carried out
Boron DIFFUSION TREATMENT (wherein, the diffusion junction depth of boron diffusion is 0.7um), carries out single side etching, then in HF after boron DIFFUSION TREATMENT
In atmosphere remove quasi-monocrystalline silicon surface on Pyrex, and by polyethylene film (PE) to the quasi-monocrystalline silicon into
Row overlay film.
Exposure mask is being carried out to quasi-monocrystalline silicon using polyethylene film (PE) and then is carrying out phosphorus diffusion (wherein, phosphorus diffusion
Junction depth is 0.35um) processing, the phosphorosilicate glass on quasi-monocrystalline silicon surface is removed in HF atmosphere.Then, single in the standard
Pellumina and SiN film (wherein, pellumina with a thickness of 20nm) is successively plated in the front of crystal silicon chip, and the back side plates SiN film
Later, it is two-sided print electrode respectively after carry out surface defect Passivation Treatment.Specifically, when carrying out defect passivation processing,
Temperature is 300 DEG C, and electric current finally obtains the surface progress defect passivation processing of the quasi- monocrystalline battery in the environment of being 18A quasi- single
Brilliant battery.Battery sorting test finally is carried out to quasi- monocrystalline battery obtained, to find out the highest battery of solar energy conversion efficiency.
In the present embodiment, the transfer efficiency of solar battery obtained can be up to 21.3%.
Embodiment five
A quasi-monocrystalline silicon is chosen first, is put into the mix acid liquor of hydrofluoric acid and nitric acid that volume ratio is 1:6 at immersion
2min is managed to remove the damaging layer on surface, wherein the temperature of the mix acid liquor is 7 DEG C.
Then, which is impregnated into 5.5min in 27 DEG C of hydrofluoric acid and the mixing liquid of hydrogen peroxide, wherein
The volume ratio of hydrofluoric acid and hydrogen peroxide is 1:2.The processing method is the black silicon making herbs into wool of wet process, primarily to by the quasi-monocrystalline silicon
Surface forms the etch pit of multiple circular holes.
Further, the potassium hydroxide and Ammonia progress that volume ratio is 1:3 are added in Xiang Suoshu mixed liquor
It neutralizes, to finally obtain neutral mixed liquor.Then the quasi-monocrystalline silicon that will be obtained after the black silicon making herbs into wool of wet process, in the neutrality mixed liquor
Middle cleaning 2min.Wherein, which mainly cleans silicon hole (etch pit).
Further, after completing prerinse, by the quasi-monocrystalline silicon 20 DEG C of hydrofluoric acid and hydrochloric acid mixing
Pickling 1min in acid solution.Wherein, the volume ratio of hydrofluoric acid and hydrochloric acid is 1:2.Use mixed liquor pair made of hydrofluoric acid and hydrochloric acid
Making herbs into wool face is cleaned, wherein hydrochloric acid is mainly used for neutralizing the remaining lye of previous step, and hydrofluoric acid is mainly used for removing surface
Silica is prepared for subsequent cleaning technology.
Chemical reaction etching is carried out to the quasi-monocrystalline silicon, the quasi-monocrystalline silicon that will be obtained after pickling, in SF6Gas atmosphere
It is reacted in enclosing, generates group containing F* and generate volatile SiF in the environment of silicon substrate4(this step is etching to gas
Effect)；Then O* group and SiF4Gas reaction generates the first passivation product SixOyFz, a passivation product SixOyFz of generation
In deposition to quasi-monocrystalline silicon, so that the continuation of F* group be prevented to be reacted with the silicon wafer on surface.Then, inclined using DC pulse
Energetic ion under pressure effect hits the first passivation product SixOyFz in quasi-monocrystalline silicon to form the first flannelette, makes F* base
Group continues to be reacted with the silicon wafer on surface, and silicon chip surface forms the suede structure of random distribution.
Further, after carrying out chemical reaction etching and physical ion bombardment processing, quasi-monocrystalline silicon is carried out
Boron DIFFUSION TREATMENT (wherein, the diffusion junction depth of boron diffusion is 0.65um), carries out single side etching, then in HF after boron DIFFUSION TREATMENT
In atmosphere remove quasi-monocrystalline silicon surface on Pyrex, and by polyethylene film (PE) to the quasi-monocrystalline silicon into
Row overlay film.
Exposure mask is being carried out to quasi-monocrystalline silicon using polyethylene film (PE) and then is carrying out phosphorus diffusion (wherein, phosphorus diffusion
Junction depth is 0.35um) processing, the phosphorosilicate glass on quasi-monocrystalline silicon surface is removed in HF atmosphere.Then, single in the standard
Pellumina and SiN film (wherein, pellumina with a thickness of 17nm) is successively plated in the front of crystal silicon chip, and the back side plates SiN film
Later, it is two-sided print electrode respectively after carry out surface defect Passivation Treatment.Specifically, when carrying out defect passivation processing,
Temperature is 250 DEG C, and electric current finally obtains the surface progress defect passivation processing of the quasi- monocrystalline battery in the environment of being 17A quasi- single
Brilliant battery.Battery sorting test finally is carried out to quasi- monocrystalline battery obtained, to find out the highest battery of solar energy conversion efficiency.
In the present embodiment, the transfer efficiency of solar battery obtained can be up to 21.5%.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (8)
1. a kind of preparation method of quasi- monocrystalline battery, for preparing the quasi- monocrystalline battery, feature based on a quasi-monocrystalline silicon
It is, which comprises
The black silicon making herbs into wool of wet process: the quasi-monocrystalline silicon is impregnated in the first mixed liquor of the first preset temperature first it is default when
Between, wherein first mixed liquor includes hydrofluoric acid and hydrogen peroxide；
Prerinse: being added the second mixed liquor to obtain neutral mixed liquor in the first mixed liquor of Xiang Suoshu, and by the quasi-monocrystalline silicon
Piece cleans the second preset time in the neutral mixed liquor, wherein second mixed liquor includes potassium hydroxide and hydroxide
Ammonium；
Pickling: when pickling third is default in the third mixed liquor of the second preset temperature by the quasi-monocrystalline silicon after prerinse
Between, wherein the third mixed liquor includes hydrofluoric acid and hydrochloric acid；
The black silicon processing of dry method: the quasi-monocrystalline silicon after pickling is successively carried out to chemical reaction etching and physical ion is banged
Hit processing；
Wherein, the step of carrying out chemical reaction etching includes: the quasi-monocrystalline silicon that will be obtained after pickling, in SF6Gas atmosphere
It is reacted in enclosing to obtain SiF4Gas；The SiF4Passivation reaction occurs between gas and the quasi-monocrystalline silicon and obtains the
After one passivation product, in the first passivation product deposition to the quasi-monocrystalline silicon；
Carry out physical ion bombardment processing the step of include:
Using the energetic ion under DC pulse bias effect, hit in the quasi-monocrystalline silicon it is described first passivation product with
Form the first flannelette；
The preparation of quasi- monocrystalline battery: by the black silicon of dry method, treated that the quasi-monocrystalline silicon successively carries out boron diffusion, phosphorus diffusion, plated film
And the quasi- monocrystalline battery is obtained after processing of printing electrode.
2. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that handle the black silicon of dry method described
After the quasi-monocrystalline silicon afterwards carries out the step of boron diffusion, the method also includes:
Single side etching is carried out to the quasi-monocrystalline silicon after the boron DIFFUSION TREATMENT；
The Pyrex on the quasi-monocrystalline silicon surface are removed in HF atmosphere, and by polyethylene film to the standard
Monocrystalline silicon piece carries out overlay film.
3. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that by the quasi-monocrystalline silicon into
After the step of row phosphorus diffusion, the method also includes:
The phosphorosilicate glass on the quasi-monocrystalline silicon surface is removed in HF atmosphere.
4. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that carried out to the quasi-monocrystalline silicon
The step of plated film includes:
After the front of the quasi-monocrystalline silicon plates one layer of pellumina, plated respectively in the front and back sides of the quasi-monocrystalline silicon
Upper layer of sin film.
5. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that the quasi-monocrystalline silicon into
Row prints electrode after processing, the method also includes:
It is 200~300 DEG C in temperature, it is blunt that electric current carries out defect to the surface of the quasi- monocrystalline battery in the environment of being 16~18A
Change processing.
6. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that the quasi-monocrystalline silicon into
Before the step of row wet process black silicon making herbs into wool, the method also includes:
The quasi-monocrystalline silicon is impregnated into 2min in 6~8 DEG C of prefabricated pickling solution, the prefabricated pickling solution includes that volume ratio is
The hydrofluoric acid and nitric acid of 1:6.
7. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that the temperature of first preset temperature
Spending range is 25 DEG C~30 DEG C, and first preset time is 5~6min.
8. the preparation method of quasi- monocrystalline battery according to claim 1, which is characterized in that second preset time is 1
~3min, second preset temperature are 20 DEG C, and the third preset time is 1min.
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