CN108511539A - A kind of solar battery sheet and preparation method thereof and solar cell - Google Patents
A kind of solar battery sheet and preparation method thereof and solar cell Download PDFInfo
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- CN108511539A CN108511539A CN201710111365.5A CN201710111365A CN108511539A CN 108511539 A CN108511539 A CN 108511539A CN 201710111365 A CN201710111365 A CN 201710111365A CN 108511539 A CN108511539 A CN 108511539A
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- solar battery
- battery sheet
- silicon substrate
- hydrofluoric acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 146
- 229910052710 silicon Inorganic materials 0.000 claims description 146
- 239000010703 silicon Substances 0.000 claims description 146
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 116
- 239000000758 substrate Substances 0.000 claims description 84
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000009792 diffusion process Methods 0.000 claims description 36
- 239000011159 matrix material Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 27
- 229910017604 nitric acid Inorganic materials 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 24
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- 239000000203 mixture Substances 0.000 claims description 16
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- 239000002923 metal particle Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
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- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 235000007164 Oryza sativa Nutrition 0.000 description 1
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- -1 silicon Alkane Chemical class 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of solar battery sheet and preparation method thereof and solar cells.The surface of the solar battery sheet has cell piece hole, and the opening width of the cell piece hole is 400~1000nm, and the depth of the cell piece hole is 100~400nm.Photoelectric conversion efficiency is high, appearance is spent without apparent crystalline substance, can extensive actual production.
Description
Technical field
The present invention relates to area of solar cell, more specifically to a kind of solar battery sheet and preparation method thereof
And solar cell.
Background technology
Solar cell photovoltaic power generation is to solve the important channel of global energy crisis and problem of environmental pollution, wherein closely
90% using silicon chip solar cell.Diamond fretsaw cutting technique starts to give birth to applied to the cutting of crystal silicon chip in recent years
Production, compared with the silicon carbide abrasive mortar line cutting technology of existing mainstream, it has, and rate of cutting is high, carrying capacity of environment is small, silicon chip
Surface mechanical damage is small, silicon sawdust is few and easy recycling, the curvature of silicon chip and the small advantage of total thickness deviation, diamond wire are cut
Polysilicon chip cost can significantly be reduced by cutting.Compared with existing mortar saw blade cutting silicon chip, diamond wire saw cut silicon
Apparent cutting line and higher surface reflectivity is presented in piece total surface.Diamond wire saw silicon chip asperity compares sand in fact
Slurry cutting silicon chip is small, therefore it is believed that these cutting lines should be unable to influence the performance of solar cell, still, photovoltaic market
Reflection shows that it cuts line and is enough to hinder its market development.Theory and practice shows in anisotropic alkaline etching making herbs into wool process
In, the diamond cutting cut pattern on monocrystalline silicon piece can be completely removed, therefore, diamond-cutting technique is in the production of monocrystalline silicon piece
On be applied.But for diamond cutting polysilicon chip, making herbs into wool is etched using conventional nitration mixture, reflectivity cannot subtract
As low as existing professional standard, and there are the open defects such as apparent stria, seriously reduces battery efficiency.Such as use alkaline etching such
Polysilicon chip has a good making herbs into wool effect to the grain surface being orientated close to (001), and micro-scratches and the reciprocal line of macroscopic view can be by
Thoroughly removal, but to no effect to the crystal grain of other orientations, and the battery efficiency being prepared is still relatively low.
To solve the problems, such as that the making herbs into wool of diamond cut silicon chip, some Japanese photovoltaic enterprises introduce sandblasting pretreatment technology, goes
Except line is cut on diamond wire saw polysilicon chip surface, but its is additional of high cost, and equipment is complicated.In addition, a small number of potential
Silicon wafer cut by diamond wire making herbs into wool technology is needed than existing producing line technical sophistication, is held high if plasma reaction etches (IRE) method
Expensive equipment, mature technology is transferred to producing line, and it will take time.
Metal ion auxiliary making herbs into wool (black silicon) technology has been developed in recent years the preferable diamond wire that solves of one kind and cutting silicon
The method of piece making herbs into wool.The technology is to form joint etching liquid using the precious metal ions such as Au, Ag, hydrogen peroxide and hydrofluoric acid,
During silicon chip erosion, metal ion at nano-particle and is attached to silicon chip surface by Si reduction, then metallic conduct
Cathode, silicon constitute micro- electrochemical reaction channel as anode in silicon face.Hydrogen peroxide, which acts on, generates dioxy on the surface of silicon
SiClx, hydrofluoric acid carry out network and effect to silica, generate water-soluble complex compound, to below nano metal particles
Quickly etching forms micro-nano hole, which has good sunken luminous effect.But in actual production, metal ion is auxiliary
It helps to form micro-nano matte, although surface reflectivity is reduced, the efficiency of battery does not get a promotion, and appearance
There is also bad, therefore, how metal ion auxiliary making herbs into wool (black silicon) technology to be applied in produce reality on a large scale, be still
Current problem in the urgent need to address.
Invention content
The present invention is in order to solve the skill that existing metal ion auxiliary making herbs into wool technology cannot be used on a large scale in actual production
Art problem, provide a kind of photoelectric conversion efficiency is high, appearance without apparent brilliant flower, can extensive actual production solar battery sheet and
Preparation method and solar cell.
It is an object of the present invention to provide a kind of solar battery sheet, the surface of the solar battery sheet has cell piece
The opening width of hole, the cell piece hole is 400~1000nm, and the depth of the cell piece hole is 100~400nm.
It is preferred that the opening width of cell piece hole is 500~800nm, the depth of the cell piece hole is 150~
300nm。
It is preferred that the bottom width of cell piece hole is less than opening width.
It is a further object to provide the preparation method of above-mentioned solar battery sheet, step includes：In silicon substrate
Surface opens up the matrix hole that opening width is 500~1200nm, depth is 200~500nm, after by spreading, adhering to anti-reflection
It penetrates film and solar battery sheet is made.
Third object of the present invention is to provide a kind of solar cells, including above-mentioned solar battery sheet.
The present inventor is had found by long-term practical studies, due to the boundary effect of silicon substrate and the shadow of crystal orientation
It rings, causes the openings of sizes of micro-nano hole, the difference of direction and depth, for follow-up diffusion, PECVD (plasma enhancings
Learn vapour deposition process) etc. the reaction gas of techniques enter hole and form obstacle.In addition, the textured surfaces product increased considerably
The complex centre that carrier can be become, causes the solar battery sheet electricity conversion of extensive actual production low.
On this basis, the present invention by specific metal ion assist making herbs into wool obtain particular size, depth it is micro-nano
Hole, the polysilicon chip after cutting diamond wire using processes such as diffusion, coated with antireflection films, which is prepared into surface, has special hole
The polycrystalline silicon solar cell piece of structure, for general solar battery sheet, including silicon substrate and the expansion for being attached to silicon substrate surface
Layer and antireflection film layer are dissipated, i.e., the present invention is obtained by the auxiliary making herbs into wool of specific metal ion on the surface of silicon substrate specific big
Small, depth matrix hole, diffusion layer and antireflection film layer at matrix hole are attached to hole wall and the bottom of matrix hole
Portion forms the cell piece hole of special pore space structure, has been surprisingly found that the opto-electronic conversion of the solar battery sheet with this special construction
Efficiency is significantly improved, and even higher than current conventional slurry cuts the cell piece that silicon chip acid making herbs into wool obtains, and appearance is cut with mortar
Silicon chip battery piece approaches, and without apparent brilliant flower phenomenon, reason supposition may be the cell piece of 1, particular size of the present invention, depth
Hole has excellent sunken optical property, cuts conventional batteries piece compared to traditional sour making herbs into wool mortar, can largely reduce light
Reflection loss.2, matrix hole of the invention makes diffusion layer and antireflection film layer be evenly distributed in hole, in hole
The good passivation effect on silicon surface layer, and the remaining nano metal particles of metal ion auxiliary making herbs into wool are also easy to be cleaned out, eliminating
The complex centre of carrier.It is especially obtained to be less than the particular size of opening width, the matrix of depth with bottom width
Hole, hole have inverted tubaeform structure, as represented in figure 1, should during the diffusion of cell piece and coated with antireflection membrane process
Structure makes working gas, it is easy to spread and the wall surface of coverage hole and bottom, from prepared by diffusion layer and antireflective coating
Layer is distributed relatively uniformly in hole, and to the good passivation effect on the silicon surface layer in hole, can further increase the sun
The performance of energy battery.In addition, the hole with the inverted tubaeform structure, remaining nano metal particles are also easier to be cleaned out
Come, eliminates the complex centre of carrier, the collecting effect of the photo-generated carrier of solar cell of the invention is good, the short circuit of battery
Electric current and open-circuit voltage are high.Solar battery sheet prepared by the present invention is not only prepared by more existing diamond wire saw cut silicon chip
Solar battery sheet efficiency significantly promoted, or even compared with the battery prepared by conventional slurry cuts silicon chip, be averaged photoelectricity
The absolute value of efficiency can also promote 0.30% or more.
Description of the drawings
Fig. 1 is the enlarged local section of micro-nano hole, that is, matrix hole of the silicon substrate prepared by the embodiment of the present invention 1
Schematic diagram, d1 are the opening width of micro-nano hole, and d2 is the width of micro-nano hole bottom surface, and h is the depth of micro-nano hole,
Angles of the α between micro-nano hole side and bottom surface.
Fig. 2 is the enlarged local section schematic diagram of the cell piece hole prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM figures (50000 times of amplification) of the matrix hole prepared by the embodiment of the present invention 1.
Fig. 4 is the SEM figures (20000 times of amplification) of the cell piece hole prepared by the embodiment of the present invention 1.
Fig. 5 is the SEM figures (50000 times of amplification) of the micro-nano hole on the silicon substrate surface prepared by comparative example 1 of the present invention.
Fig. 6 is the SEM figures (10000 times of amplification) in the micron hole on the silicon substrate surface prepared by comparative example 4 of the present invention.
Fig. 7 is the outside drawing in kind of the silicon substrate prepared by the embodiment of the present invention 1.
Fig. 8 is the outside drawing in kind of the silicon substrate prepared by comparative example 1 of the present invention.
Fig. 9 is the outside drawing in kind of the silicon substrate prepared by comparative example 4 of the present invention.
Figure 10 is the outside drawing in kind of the solar cell piece prepared by the embodiment of the present invention 1.
Figure 11 is the outside drawing in kind of the solar cell piece prepared by comparative example 1 of the present invention.
Figure 12 is the outside drawing in kind of the solar cell piece prepared by comparative example 4 of the present invention.
Specific implementation mode
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below in conjunction with
Accompanying drawings and embodiments, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
The present invention provides a kind of solar battery sheet, and the surface of the solar battery sheet has cell piece hole, the electricity
The opening width of pond piece hole is 400~1000nm, and the depth of the cell piece hole is 100~400nm.Further preferably,
The opening width of cell piece hole is 500~800nm, and the depth of the cell piece hole is 150~300nm.It can significantly improve
The photoelectric conversion efficiency of solar cell and the solar battery sheet appearance of preparation are without apparent brilliant flower.
It is preferred that the bottom width of cell piece hole is less than opening width.Such as inverted tubaeform structure, as shown in Fig. 2,
D2 is less than d1, can largely reduce the reflection loss of light.General solar battery sheet, including silicon substrate and it is attached to silicon
The diffusion layer and antireflection film layer of matrix surface, can be by opening up the matrix hole of such shape on silicon substrate surface, then prepares
Such solar battery sheet can be obtained in uniform diffusion layer and antireflection film layer.The photo-generated carrier of the solar cell of the present invention
Collecting effect is good, and the short circuit current and open-circuit voltage of battery are high, compared with the battery prepared by conventional slurry cuts silicon chip, is averaged
The absolute value of photoelectric efficiency can promote 0.30% or more.
Further preferably, as shown in Fig. 2, the angle α of the side and bottom surface of cell piece hole is 100 °~135 °, into one
Step is preferred, and the side of cell piece hole and the angle of bottom surface are 110 °~120 °, advanced optimize pore space structure, specific to be open
The solar cell piece performance that width, gradient and depth obtain is more excellent.
Solar battery sheet generally comprises silicon substrate and the diffusion layer and antireflection film layer that are attached to silicon substrate surface, described
The surface of silicon substrate has matrix hole, and diffusion layer and antireflection film layer at matrix hole are attached to the side of matrix hole
Above-mentioned cell piece hole is formed on face and bottom surface, that is, hole wall and bottom.It is preferred that the opening width of matrix hole is 500~1200nm,
Preferably 600~1000nm；The depth of matrix hole is 200~500nm, preferably 300~400nm.Make diffusion layer and anti-reflection
It penetrates film layer to be evenly distributed in hole, to the good passivation effect on the silicon surface layer in hole, and metal ion assists the remnants of making herbs into wool
Nano metal particles are also easy to be cleaned out, eliminating the complex centre of carrier.
It is preferred that the thickness of antireflection film layer is 80~90nm.
Invention also provides a kind of preparation method of solar battery sheet, step includes：It is opened up on silicon substrate surface
The matrix hole that opening width is 500~1200nm, depth is 200~500nm, after through diffusion, adhere to antireflective coating be made
Solar battery sheet.
Specific steps may include：
S11, deposited metal particle：Silicon substrate is placed in deposited metal in the salt of metal ion and the mixed liquor of hydrofluoric acid
Particle；It is specifically as follows salt (such as AgNO that silicon substrate is placed in metal ion3) and the mixing liquid bath of hydrofluoric acid in, make metal
Ion at nano metal particles and is deposited on silicon substrate surface by Si reduction.It is preferred that in this step S11, the salt of metal ion
And in the mixed liquor of hydrofluoric acid metal ion a concentration of 10~100ppm, volumetric concentration of the hydrofluoric acid in mixed liquor be 0.5
~10%；Wherein, the mass concentration of the hydrofluoric acid is 49~50%；The nano metal particles grain size of generation is advanced optimized,
And the distribution on silicon substrate surface.It is preferred that the reaction temperature of this step is 20~30 DEG C, the reaction time is 50~150s.It is general anti-
120~240s can be cleaned after the completion of answering with deionized water.
It is preferred that further including carrying out pre-treatment to silicon substrate before step S11, there is no limit can be ability to the pre-treatment present invention
Various pre-treatments, the present invention well known to field technique personnel are preferably：
S01, alkali are just thrown；It is preferred that sodium hydroxide or potassium hydroxide solution are specially used, at a certain temperature, by polycrystalline
Body silicon substrate carries out initial burnishing, to remove the greasy dirt and damaging layer of silicon face, so that silicon substrate surface is formed opposed flattened micro-
Then rice matte crosses deionized water and cleans 120~240s.In this stage, the mass concentration of highly basic can control 2.0~
15wt%, temperature can be controlled at 60~90 DEG C, and the reaction time can be 1.0~5.0min, and average loss of weight amount can be 0.20
~0.35g can more preferably remove the damaging layer that silicon wafer cut by diamond wire leaves.
S02, acid cleaning；Use volumetric concentration for 0.2~2.0% silicon substrate obtained by step S01 it is preferred that being specifically as follows
Dust technology cleaning silicon substrate on remaining highly basic, cleaning temperature can be room temperature, scavenging period be 50~100 seconds, then again
It crosses deionized water and cleans 120~240s.
S21 opens micro-nano hole：Silicon substrate obtained by step S11 is placed in the etching liquid of hydrofluoric acid containing and hydrogen peroxide and is etched；
The volume of hydrogen peroxide in the etching liquid：The volume of hydrofluoric acid：The volume of water=(2~5)：1：(5~8), in this step S21 on
The mass concentration for stating hydrogen peroxide is 30~32%；The mass concentration of hydrofluoric acid is 49~50%；Use the double of this mass concentration
Oxygen water, hydrofluoric acid configure etching liquid by above-mentioned volume ratio.It is specifically as follows and silicon substrate is positioned over hydrofluoric acid containing and hydrogen peroxide
In etching liquid groove.Step S11 is deposited on the nano metal particles on silicon substrate surface as cathode, silicon as anode, in silicon substrate
Surface constitutes micro- electrochemical reaction channel, and hydrogen peroxide and hydrofluoric acid joint are used as etching liquid, hydrogen peroxide to act on raw on silicon
At silica, hydrofluoric acid carries out network and effect to silica, generates water-soluble complex compound, in nano metal particles
Quickly etching forms micro-nano pore space structure for sub- lower section, because of the anisotropy of etching, the opening shape of the micro-nano hole of formation with
Crystal orientation is related, and in (100), crystal orientation generally forms quadrangle micro-nano hole, and in (111), crystal orientation generally forms hexagon micro-nano hole
Deng.
For same crystal orientation, crystal boundaries are removed, etching liquid is roughly the same to the corrasion of the silicon of the crystal orientation, therefore,
Shape, width (distance for referring to two parallel edges of quadrangle or hexagon), the depth in the hole of same crystal orientation are essentially identical.
For different crystal orientation, the size and depth of trepanning can be controlled by adjusting the concentration, temperature or time of etching liquid.The present invention
Pass through the volume of hydrogen peroxide：The volume of hydrofluoric acid：The volume of water=(2~5)：1：(5~8), the body of further preferred hydrogen peroxide
Product：The volume of hydrofluoric acid：The volume of water=(3~5)：1：(5~8), to which the matrix hole of unique size, depth be made.Into
One step is preferred, this step reaction temperature is 30~40 DEG C, and etch period is 200~300s.Suitable hole is not only avoided that follow-up
The difficulty of battery process increases, and avoids falling into luminous effect, optimizes the efficiency of cell piece.Generally, after the completion of trepanning, by silicon substrate
It crosses deionized water and cleans 120~240s.
S31 cuts expansion micro-nano hole：Silicon substrate obtained by step S21 is placed in the mix acid liquor containing nitric acid and hydrofluoric acid, institute
State the volume of nitric acid in mix acid liquor：The volume of hydrofluoric acid：The volume of water=(5.0~9.0):1:(7~10)；In step S31
The mass concentration of the nitric acid is 65~68%；The mass concentration of the hydrofluoric acid is 49~50%；Use this mass concentration
Nitric acid, hydrofluoric acid by above-mentioned volume ratio configure mix acid liquor.It is specifically as follows and silicon substrate is positioned over containing nitric acid and hydrofluoric acid
Mixed acid liquid bath in, joint etching is carried out to the micro-nano hole that silicon substrate surface etch is formed by nitric acid and hydrofluoric acid, is adopted
Opened micro-nano hole is etched with the mix acid liquor of high concentration and high rich nitric acid, the hole depth of micro-nano hole can be reduced, meanwhile,
Micro-nano hole is advanced optimized, the opening shape and size of micro-nano hole are optimized, has been surprisingly found that the mixed of high concentration and high rich nitric acid
Closing acid solution makes original quadrangle or hexagonal corner angle be passivated to form arc chord angle, makes the opening of micro-nano micropore by original four
Side shape or hexagon become quasi-circular, and (quasi-circular of the invention refers to its similar circle, because the seamed edge of former polygon is not etched, only
Corner angle are etched to circular arc, and the width of quasi-circular refers to the radial width by central point), while can further reaming.
Since the depth of micro-nano hole is deeper, mix acid liquor enters hole domestic demand and wants the regular hour, therefore the appearance of micro-nano hole
Face edge and wall surface are preferentially etched, and under high concentration and the mix acid liquor system of high rich nitric acid, etching liquid has silicon substrate
Very high etching speed, to form (being reamed one layer of micro-nano hole thereon) etching on remaining micro-nano hole
Outer width is narrow, with inverted tubaeform shape (from silicon face it is outer inwards from) quasi- truncated cone-shaped micro-nano hole, as shown in Figure 3.
The volume of the preferred nitric acid of the present invention：The volume of hydrofluoric acid：The volume of water=(6.0~8.0):1:(8~9), this hair
It is bright using the mix acid liquor containing specific nitric acid and hydrofluoric acid concentration to be made specific shape pore space structure, preferably nitric acid with
The concentration proportion γ of hydrofluoric acid is 5~9, further preferred 6~8, under same total acid concentration.If γ is small, speed is reacted
It is slow to spend, then the top and bottom etching speed of micropore is close, i.e., cannot form the hole of inverted tubaeform shape, at this time the inclined surface in hole
Angle α with bottom surface is for 90 ° or close to 90 ° (α=90 ° are quasi-cylindrical holes), as shown in Figure 5.γ is bigger, and reaction speed is got over
Soon, top surface (opening) the width d1 of the micro-nano hole of quasi- truncated cone-shaped differs bigger with bottom width d2, i.e. the angle α in hole is got over
Greatly, light incidence back reflection go out hole amount it is more, reflectivity is also bigger, also more has with coating process to subsequent diffusion
Profit.Certain γ can not be too big, and otherwise the α in hole is too big, and light is easy to be reflected, and falls into light efficiency strain differential, loses micro-nano hole
Compared to the advantage in conventional micron hole.
It is preferred that this step reaction temperature is 8~13 DEG C, optimal is 9~11 DEG C, and the reaction time is 80~180s, and optimal is 100
~150s.Micro-nano hole structure is advanced optimized, avoids average reflectance from increasing and generates brilliant flower phenomenon, while simplifying technique.
It is preferred that monolithic silicon substrate subtracts Weight control in 0.06~0.15g before and after this process, optimum range is 0.08~0.12g, into
The performance of one-step optimization solar battery sheet.
Generally, it cuts to expand after micro-nano hole and silicon substrate is also crossed into 120~240s of deionized water cleaning.
S41, porous silicon and micro-nano hole amendment are removed：Silicon substrate obtained by step S31 is placed in lye and removes porous silicon layer
And micro-nano hole is modified.It is preferred that the lye is molten for the sodium hydroxide or potassium hydroxide of mass concentration 0.2~5.0%
Liquid, the time being placed in lye are 5.0~30s.Be specifically as follows silicon substrate is placed on it is molten containing sodium hydroxide or potassium hydroxide
It is performed etching in the slot of liquid, the highly basic of low concentration rapidly removes the loose Porous Silicon structures of silicon extexine, and exposing has this hair
The matte of the micro-nano hole formation of quasi- truncated cone-shaped of bright feature.It is preferred that reaction temperature is room temperature, the reaction time is 5.0~30s,
The micro-nano hole after expanding micro-nano hole is cut in this step to be destroyed, and shape does not have big variation with volume.Generally, it reacts
After the completion, silicon substrate is crossed into deionized water and cleans 120~240s.
S51, removal metallic.Silicon substrate obtained by step S41 is preferably placed in the solution containing ammonium hydroxide and hydrogen peroxide
In.It is specifically as follows and silicon substrate obtained by step S41 is put into the mixing liquid bath containing ammonium hydroxide and hydrogen peroxide, the volume of ammonium hydroxide：It is double
The volume of oxygen water：Volume=1 of water：(1~4)：(40~50)；The mass concentration of ammonium hydroxide described in this step S41 be 25~
28%, the mass concentration of the hydrogen peroxide is 30~32%；Such as upper body is pressed using the ammonium hydroxide of above-mentioned mass concentration and hydrogen peroxide
Product configuration mixed liquor, hydrogen peroxide is oxidant, nano metal (such as silver) particle that preamble cleaning does not remove is aoxidized, using ammonia
Water is complexing agent, forms it into silver-colored amine complex ion and is dissolved in water and is removed.It is preferred that the temperature of reaction is room temperature, the time of reaction
For 50~300s, silicon substrate can generally, after having reacted be crossed to deionized water and clean 120~240s.
Further include after the step S51：
S52, nitration mixture cleaning.Be specifically as follows silicon substrate obtained by step S51 is positioned over hydrofluoric acid containing and hydrochloric acid acid it is molten
It is cleaned in liquid, to remove other trace metal impurities (such as iron, nickel metal impurities), object in the acid solution of hydrofluoric acid containing and hydrochloric acid
Matter Volume fraction is hydrochloric acid：Hydrofluoric acid：Water=(2~3)：1：(5~6), the mass concentration of hydrochloric acid described in this step S52 are
35~38%, the mass concentration of the hydrofluoric acid is 49~50%.It is preferred that the temperature of reaction be room temperature, scavenging period be 50~
300s.After General reactions, silicon substrate can be crossed to deionized water and clean 120~240s.
S53 is slow to lift.Be specifically as follows by silicon substrate obtained by step S52 using heat deionized water cleaning 120~
240s, water temperature are 60~80 DEG C, and then slowly lifting, silicon substrate is left the water.The lifting time is 5~20s.It is general controllable
The survivor ion concentration of water, the resistance value of deionized water in the slot is tested using conductivity meter in slot, controls it at 70 ± 2 DEG C
The μ S/cm of conductivity value≤1.0.
S54, it is dry, it is specifically as follows silicon substrate body heat drying obtained by step S53, drying temperature is 100~150 DEG C, when
Between be 5~15min.
It is preferred that concentration≤50ppb of gained silicon substrate surface metal atoms or ion after dry, using inductive coupling etc. from
Daughter mass spectrograph (ICP-MS) is tested.The silicon substrate of special construction of the present invention makes remnants due to the matrix hole of surface special construction
Nano metal particles are few, eliminate the complex centre of carrier, can improve electricity conversion.
Be embodied above-mentioned steps after to get to Buddha's warrior attendant wire cutting silicon substrate carry out making herbs into wool after silicon substrate, such as Fig. 7 institutes
Show that no crystal boundary phenomenon is detected using matte reflectance meter, in 400~1100nm as can be seen that the silicon substrate surface wool manufacturing is uniform
In wave band, be averaged light reflectivity 14~22%, it is preferable that 16~20%.Under scanning electron microscope (SEM), this hair is observed
The matte of the silicon substrate of bright preparation, it can be seen that the matte is by with the micro- of certain opening width, angle of inclination and hole depth
Nano aperture is constituted.
S61, diffusion.There is no limit may be used that well known to a person skilled in the art various diffusions to the diffusion technique present invention
Technique, details are not described herein.After preparing the silicon substrate with feature of present invention matte, makes it into diffusion furnace and expand by phosphorus
PN junction processed is dissipated, it is roughly the same that diffusion technique with the mortar of conventional acid making herbs into wool cuts silicon chip.Because of the quasi- truncated cone-shaped micro-nano hole of the present invention
Hole has inverted tubaeform structure, and in diffusion process, phosphorus source gas is easy to wall surface and the bottom of diffusion and coverage hole, makes in this way
It obtains n type diffused layer to be evenly distributed along hole, the effects of N layers of collection carrier are good, and the open-circuit voltage and short circuit current of battery are high.This
In invention, the temperature or phosphorus source amount of diffusion are adjusted, makes the average sheet resistance of the silicon chip after diffusion in 80~100 Ω/, it is optimal 85
The matte of~90 Ω/, such sheet resistance range and feature of present invention has preferable matching degree.
It is preferred that further including after step S61：
S62, phosphorosilicate glass is removed.Generally secondary cleaning goes phosphorosilicate glass, removal phosphorosilicate glass layer and etching silicon substrate week
Side, the technique present invention there is no limit, may be used that well known to a person skilled in the art various etching technics, it is no longer superfluous herein
It states.
S71, coated with antireflection film.PECVD plates SiNxAntireflective coating.There is no limit may be used this to the coating process present invention
Various coating process well known to field technology personnel, details are not described herein.The matrix hole of the special construction of above-mentioned preparation makes silicon
Alkane gas and ammonia can smoothly enter into inside hole so that there is aperture wall and bottom good blunt atomic hydrogen in coating process
Change effect, greatly reduces due to the dangling bonds that silicon generates in etching making herbs into wool process Hole, reduce complex centre number, electricity
The open-circuit voltage and short circuit current in pond all obtain certain promotion, it is preferable that 80~90nm of thickness of antireflection film layer, mean refraction
Rate 2.00~2.20.
S81, electrode of solar battery is prepared.It generally prints electrode and metallizes and light-receiving surface electrode and shady face electricity is made
Pole is used for extracted current, and various electrode structures may be used in light-receiving surface electrode and shady face electrode, for example, can overleaf print
Aluminium paste, back silver paste are carried on the back, front prints positive silver paste and obtains the solar battery sheet with positive and negative electrode after sintering furnace.
Invention also provides a kind of solar cells, including above-mentioned solar battery sheet.Solar cell other
Structure is known, and details are not described herein.
In order to make the technical problems, technical solutions and beneficial effects solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining this
Invention, is not intended to limit the present invention.
Embodiment 1
Raw material agent class, concentration used by the present embodiment are respectively：Potassium hydroxide, electron level, mass concentration are
45%；Nitric acid：Electron level, mass concentration are 65~68%, hydrofluoric acid：Electron level, mass concentration are 49~50%；Silver nitrate：
Analyze pure, solid, purity 99.9%；Ammonium hydroxide：Electron level, mass concentration are 25~28%；Hydrogen peroxide, electron level, quality are dense
Degree is 30~32%；Hydrochloric acid：Electron level, mass concentration are 35~38%；
Using 156 × 156 polysilicon chips of Buddha's warrior attendant wire cutting, its resistivity value ranging from 1.20~2.50 Ω are tested
Cm meets the resistivity requirement of silicon chip.It is 1.10~1.60 μ s to test its minority carrier life time numberical range, meets few sub- longevity of silicon chip
Life requires.It is tested every time using 200 (2 gailys decorated basket, each baskets 100), experimental result is averaged, and each technology groove holds
Product volume is 120 liters or so.Under the processing step of entire making herbs into wool process is：
A (alkali is just thrown)：15L potassium hydroxide solutions are added in just throwing slot, the water of 105L are added, obtaining mass concentration is
Solution is warming up to 80 DEG C, silicon chip is put into wherein by 7.83% potassium hydroxide solution, etch period 4.0min.It has etched
The silicon chip past is cleaned 150s from water, obtains the polysilicon chip of degreasing and damaging layer by Cheng Hou.The electronic scale weighing process subtracts
Weight is 0.282g/ pieces.
B (acid cleaning)：The silicon chip of upper step is put into rinse bath, the cleaning solution in the slot is with volumetric concentration 1%
The silicon chip past is cleaned 150s by dust technology, scavenging period 2min from water.
C (deposited metal particle)：The silicon chip of upper step is put into deposited metal particle slot, in the deposited metal particle slot
Hydrofluoric acid be added is 4L, and water 116L adds the silver nitrate crystal of 4g, obtains a concentration of 33.4ppm of silver nitrate, heating tank
The temperature of middle solution is to 20 ± 1 DEG C, reaction time 60s.It is after the completion of reaction, the silicon chip past is floating to remove from water cleaning 10s
Silver particles.
D (opens micro-nano hole):The silicon chip of upper step is placed in opening slot, which is added hydrofluoric acid 10L, hydrogen peroxide 40L,
Deionized water 70L, the volume of hydrogen peroxide：The volume of hydrofluoric acid：Volume=4 of water：1：7；Temperature is raised to 35 DEG C, the reaction time
For 240s, after the completion of reaction, the silicon chip past is cleaned into 150s from water.
E (cuts and expands micro-nano hole)：The silicon chip of upper step is placed on to cut and is expanded in micro-nano hole slot, nitric acid and hydrofluoric acid in slot
Mass volume ratio be nitric acid：Hydrofluoric acid：Water=7:1:9, the temperature of mix acid liquor is 10 DEG C, and the reaction time is 120 seconds, reaction
Silicon chip is taken out after the completion, and the silicon chip past is cleaned into 150s from water, is 0.103g/ pieces with the loss of weight amount of the electronic scale weighing process.
F (except porous silicon and micro-nano hole amendment)：The silicon chip of upper step is put into the slot added with sodium hydroxide and is carried out
Reaction is corrected, the wherein mass concentration of sodium hydroxide is 2.0%.Reaction temperature is 20 DEG C, reaction time 15s, and reaction is completed
Afterwards, the silicon chip past is cleaned into 150s from water.
G (removal metallic)：By the silicon chip of upper step be put into the mixing liquid bath added with ammonium hydroxide and hydrogen peroxide into
It goes and cleans nano silver particles, the volumetric concentration of ammonium hydroxide is 3% in slot, and the volumetric concentration of hydrogen peroxide is 5%.The temperature of solution is
20 DEG C, scavenging period is 200 seconds, and the silicon chip past is then cleaned 150s from water.
H (nitration mixture cleaning)：Silicon chip after upper step is placed in hydrofluoric acid and mixed in hydrochloric acid acid solution and is cleaned, mixed liquor
The volumetric concentration of middle hydrofluoric acid is 10%, and hydrochloric acid volumetric concentration is 20%, and the temperature of solution is 20 DEG C, pickling time 200s,
The silicon chip past is then cleaned into 150s from water.
I (slow lifting)：Silicon chip after upper step is cleaned is gone using heat from water cleaning 150s, and the temperature of water is 70 DEG C,
Then slowly lifting, silicon chip is left the water, and the lifting time is 10s, and deionized water is tested in the slot 69 using conductivity meter
DEG C when conductivity value in 0.50~0.70 μ S/cm.
J (drying)：Silicon chip after upper step is cleaned is dried using heat, and drying temperature is 120 DEG C, time 10min.
Implement after above-mentioned steps to get to the 1 sample SA1 of silicon substrate obtained by the present embodiment, using scanning electron microscope (SEM)
SA1 is observed, amplifies 50000 times, as a result such as Fig. 3.The appearance of SA1 such as Fig. 7.
Using a concentration of 17.30PPb of the remaining silver particles on its surface of ICP-MS instrument tests.
K (diffusion)：1 sample SA1 of silicon substrate after upper step is dried, which enters, passes through phosphorus diffusion PN junction in diffusion furnace.
L (removes phosphorosilicate glass)：By upper step by diffusion silicon chip by secondary cleaning with etch removal phosphorosilicate glass and
Surrounding diffusion layer.
By upper step, by the silicon chip of diffusion, the PECVD after cleaning twice plates SiN to M (coated with antireflection film)xAntireflective coating,
The average thickness of antireflective coating is 82nm, mean refractive index 2.10.
N (prepares electrode of solar battery)：By the silicon chip back side printing back of the body aluminium paste after upper step plated film, back silver paste, front
Positive silver paste is printed, the polycrystalline silicon solar cell piece sample SS1 of the present invention is obtained after burning freezing of a furnace, as shown in Fig. 2, the sun obtained
Energy cell piece includes silicon substrate 1 and is attached to the diffusion layer 2 and antireflection film layer 3 on 1 surface of silicon substrate, the table of the silicon substrate 1
Face have matrix hole 4, diffusion layer 2 and antireflection film layer 3 at matrix hole 4 be attached to matrix hole 4 side and
Cell piece hole 5 is formed on bottom surface, that is, hole wall and bottom, and the present embodiment is formed in coated with antireflection membrane process on 2 surface of diffusion layer
Hydrogen passivation layer 6 also has hydrogen passivation layer 6 in diffusion layer 2 and antireflection film layer 3.
Using scanning electron microscopic observation SS1, amplify 20000 times, as a result such as Fig. 4.The appearance of SS1 such as Figure 10.
Embodiment 2
Solar cell sample SS2 is prepared using method and step same as Example 1, the difference is that step E (it is micro- to cut expansion
Nano-pore) in the mass volume of nitric acid and hydrofluoric acid ratio be changed to nitric acid：Hydrofluoric acid：Water=5:1:10, silicon substrate sample is made
SA2。
Embodiment 3
Solar cell sample SS3 is prepared using method and step same as Example 1, the difference is that step E (it is micro- to cut expansion
Nano-pore) in the mass volume of nitric acid and hydrofluoric acid ratio be changed to nitric acid：Hydrofluoric acid：Water=9:1:9, silicon substrate sample SA3 is made.
Embodiment 4
Solar cell sample SS4 is prepared using method and step same as Example 1, the difference is that step E (it is micro- to cut expansion
Nano-pore) in the mass volume of nitric acid and hydrofluoric acid ratio be changed to nitric acid：Hydrofluoric acid：Water=8:1:7, silicon substrate sample SA4 is made.
Embodiment 5
Solar cell sample SS5 is prepared using method and step same as Example 1, the difference is that step E (it is micro- to cut expansion
Nano-pore) reaction time be 150s, silicon substrate sample SA5 is made.
Embodiment 6
Solar cell sample SS6 is prepared using method and step same as Example 1, the difference is that step D (opens micro-nano
Metre hole) in hydrogen peroxide volume：The volume of hydrofluoric acid：Volume=3 of water：1：8, silicon substrate sample SA6 is made.
Comparative example 1
Solar cell sample DSS1 is prepared using method and step same as Example 1, the difference is that step E (cuts expansion
Micro-nano hole) in the mass volume of nitric acid and hydrofluoric acid ratio be changed to nitric acid：Hydrofluoric acid：Water=4:1:10, silicon substrate sample is made
DSA1 amplifies 50000 times using scanning electron microscopic observation DSA1, as a result such as Fig. 5.The appearance of DSA1 such as Fig. 8.The appearance of DSS1 is such as
Figure 11.
Comparative example 2
Solar cell sample DSS2 is prepared using method and step same as Example 1, the difference is that step E (cuts expansion
Micro-nano hole) reaction time be 200s, silicon substrate sample DSA2 is made.
Comparative example 3
Solar cell sample DSS3 is prepared using method and step same as Example 1, the difference is that step D (is opened micro-
Nano-pore) in hydrogen peroxide volume：The volume of hydrofluoric acid：Volume=6 of water：1：7, silicon substrate sample DSA3 is made.
Comparative example 4
156 × 156 polysilicon chips cut using mortar prepare polysilicon suede using traditional nitration mixture on Rena chain type machines
Face (i.e. a cleaning), obtains silicon substrate sample DSA4, using scanning electron microscopic observation DSA4, amplifies 10000 times, as a result such as
Attached drawing 6；The appearance of DSA4 such as Fig. 9；Through 1 identical K (diffusion) of embodiment, L (removing phosphorosilicate glass), M (coated with antireflection film), N (systems
Standby electrode of solar battery) preparation process obtain solar cell piece sample DSS4.The appearance of DSS4 such as Figure 12.
Performance test
The characterization of silicon substrate SA1-SA6 and DSA1-DSA4：Under scanning electron microscope (SEM), observes and test silicon substrate
The micro-nano hole of body SA1-SA6 and DSA1-DSA4, form parameter have：Top surface opening width (d1, unit：Nm), side with
Angle (α, unit between bottom surface：Degree), depth (h, the unit of hole：nm).It is obtained using the detection of matte reflectance meter is made
Silicon substrate, in 400~1100nm wave bands average light reflectivity (Unit：%).
Electrical performance of cell parameter：It is tested using solar cell piece special test equipment, such as single flash operation simulator.
Test condition is standard test condition (STC)：Light intensity：1000W/m2；Spectrum：AM1.5；Temperature：25.Test method according to
IEC904-1 is carried out.The main unit for electrical property parameters of cell piece：Electricity conversion (Eta, unit：%), short circuit current (Isc, list
Position：A), open-circuit voltage (Voc, unit：V), (fill factor (FF, unit：%), leakage current (IRev2, unit：A), series electrical
Hinder (Rs, unit：M Ω), parallel resistance (Rsh, unit：Ω).
The characterization parameter test result of silicon substrate such as table 1：
Table 1
Electrical performance of cell parameter testing result such as table 2.
Table 2
| Sample | Eta | Isc | Voc | FF | IRev2 | Rs | Rsh |
| SS1 | 19.08 | 9.1055 | 0.6324 | 80.74 | 0.3098 | 0.00105 | 556.673 |
| SS2 | 18.85 | 8.9481 | 0.6318 | 80.51 | 0.2753 | 0.00119 | 414.774 |
| SS3 | 18.90 | 8.9842 | 0.6317 | 80.76 | 0.3267 | 0.00110 | 573.820 |
| SS4 | 18.97 | 8.9991 | 0.6315 | 80.57 | 0.2750 | 0.00109 | 402.778 |
| SS5 | 18.92 | 8.9671 | 0.6316 | 80.72 | 0.3067 | 0.00121 | 512.820 |
| SS6 | 18.80 | 8.9521 | 0.6319 | 80.65 | 0.4821 | 0.00110 | 237.000 |
| DSS1 | 18.49 | 8.8425 | 0.6305 | 80.70 | 0.5479 | 0.00130 | 386.774 |
| DSS2 | 18.56 | 8.8372 | 0.6319 | 80.87 | 0.3336 | 0.00114 | 277.572 |
| DSS3 | 18.27 | 8.7574 | 0.6293 | 80.68 | 0.3478 | 0.00094 | 229.732 |
| DSS4 | 18.44 | 8.7821 | 0.6311 | 80.73 | 0.4370 | 0.00180 | 299.042 |
As can be seen from Table 2, the short circuit current of the cell piece prepared by the embodiment of the present invention compares traditional mortar
Piece battery (comparative example DSS4) has obtained larger amplitude and has been promoted, and in 150mA or more, open-circuit voltage also has a certain range of
It is promoted, therefore the transfer efficiency of battery has been significantly improved, 0.30% or more.Cell piece effect obtained by comparative example
Rate is relatively low, do not use the cell piece open-circuit voltage of the cell piece hole of special construction of the present invention occur it is apparent decline (such as
The open-circuit voltage of DSS3 has dropped 3mV or more).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should be included in protection scope of the present invention made by within refreshing and principle.
Those skilled in the art are readily apparent that the foregoing is merely illustrative of the preferred embodiments of the present invention, not limiting
The system present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should be included in
Within protection scope of the present invention.Protection scope of the present invention is determined by claims.
Claims (17)
1. a kind of solar battery sheet, which is characterized in that the surface of the solar battery sheet has cell piece hole, the electricity
The opening width of pond piece hole is 400~1000nm, and the depth of the cell piece hole is 100~400nm.
2. solar battery sheet according to claim 1, which is characterized in that the opening width of the cell piece hole is
The depth of 500~800nm, the cell piece hole are 150~300nm.
3. solar battery sheet according to claim 1, which is characterized in that the bottom width of the cell piece hole is less than
Opening width.
4. solar battery sheet according to claim 1, which is characterized in that the side of the cell piece hole and bottom surface
Angle is 100 °~135 °.
5. solar battery sheet according to claim 4, which is characterized in that the side of the cell piece hole and bottom surface
Angle is 110 °~120 °.
6. solar battery sheet according to claim 1, which is characterized in that the solar battery sheet include silicon substrate and
It is attached to the diffusion layer and antireflection film layer on silicon substrate surface, the surface of the silicon substrate has matrix hole, described matrix hole
The opening width in hole is 500~1200nm, and the depth of described matrix hole is 200~500nm；Diffusion at matrix hole
Layer and antireflection film layer are attached to the side of matrix hole and bottom surface and form the cell piece hole.
7. solar battery sheet according to claim 6, which is characterized in that the opening width of described matrix hole is 600
The depth of~1000nm, described matrix hole are 300~400nm.
8. solar battery sheet according to claim 6, which is characterized in that the thickness of the antireflection film layer be 80~
90nm。
9. a kind of preparation method of solar battery sheet as described in claim 1-8 any one, which is characterized in that step packet
It includes：Open up the matrix hole that opening width is 500~1200nm, depth is 200~500nm on silicon substrate surface, after through expansion
It dissipates, solar battery sheet is made in attachment antireflective coating.
10. the preparation method of solar battery sheet according to claim 9, which is characterized in that step includes：S11, deposition
Metallic：Silicon substrate is placed in deposited metal particle in the salt of metal ion and the mixed liquor of hydrofluoric acid；
S21 opens micro-nano hole：Silicon substrate obtained by step S11 is placed in the etching liquid of hydrofluoric acid containing and hydrogen peroxide and is etched；It is described
The volume of hydrogen peroxide in etching liquid：The volume of hydrofluoric acid：The volume of water=(2~5)：1：(5~8)；Dioxygen described in step S21
The mass concentration of water is 30~32%；The mass concentration of the hydrofluoric acid is 49~50%；
S31 cuts expansion micro-nano hole：Silicon substrate obtained by step S21 is placed in the mix acid liquor containing nitric acid and hydrofluoric acid, it is described mixed
Close the volume of nitric acid in acid solution：The volume of hydrofluoric acid：The volume of water=(5.0~9.0):1:(7~10)；Described in step S31
The mass concentration of nitric acid is 65~68%；The mass concentration of the hydrofluoric acid is 49~50%；
S41, porous silicon and micro-nano hole amendment are removed：Silicon substrate obtained by step S31 is placed in lye and removes porous silicon layer and right
Micro-nano hole is modified；
S51, removal metallic；
S61, diffusion；
S71, coated with antireflection film；
S81, electrode of solar battery is prepared；
Solar battery sheet is made.
11. the preparation method of solar battery sheet according to claim 10, which is characterized in that carved in the step S21
The time of erosion is 200~300s.
12. the preparation method of solar battery sheet according to claim 10, which is characterized in that mixed in the step S31
Close the volume of nitric acid in acid solution：The volume of hydrofluoric acid：The volume of water=(6.0~8.0):1:(8~9).
13. the preparation method of solar battery sheet according to claim 10, which is characterized in that set in the step S31
Time in mix acid liquor is 80~180s, and the temperature of mix acid liquor is 8~13 DEG C.
14. the preparation method of solar battery sheet according to claim 10, which is characterized in that institute in the step S41
State the sodium hydroxide or potassium hydroxide solution that lye is mass concentration 0.2~5.0%, be placed in time in lye be 5.0~
30s。
15. the preparation method of solar battery sheet according to claim 10, which is characterized in that contain in the step S11
A concentration of 10~100ppm of metal ion in the salt of metal ion and the mixed liquor of hydrofluoric acid, body of the hydrofluoric acid in mixed liquor
Product a concentration of 0.5~10%；Wherein, the mass concentration of the hydrofluoric acid is 49~50%；
The removal metallic of the step S51 is that silicon substrate obtained by step S41 is placed in the solution containing ammonium hydroxide and hydrogen peroxide
In.
16. the preparation method of solar battery sheet according to claim 10, which is characterized in that before the step S11 also
Including carrying out pre-treatment to silicon substrate：
S01, alkali are just thrown；
S02, acid cleaning；
Further include after the step S51：
S52, nitration mixture cleaning；
S53 is slow to lift；
S54 is dry；
Further include after the step S61：
S62, phosphorosilicate glass is removed.
17. a kind of solar cell, which is characterized in that include the solar battery sheet as described in claim 1-8 any one.
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