CN109638088A - Solar battery and preparation method thereof and etching method - Google Patents
Solar battery and preparation method thereof and etching method Download PDFInfo
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- CN109638088A CN109638088A CN201811580939.4A CN201811580939A CN109638088A CN 109638088 A CN109638088 A CN 109638088A CN 201811580939 A CN201811580939 A CN 201811580939A CN 109638088 A CN109638088 A CN 109638088A
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 238000005530 etching Methods 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 51
- 239000010703 silicon Substances 0.000 claims abstract description 50
- 235000008216 herbs Nutrition 0.000 claims abstract description 49
- 210000002268 wool Anatomy 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 34
- 239000003153 chemical reaction reagent Substances 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000001020 plasma etching Methods 0.000 claims description 10
- 238000003487 electrochemical reaction Methods 0.000 claims description 4
- 238000002310 reflectometry Methods 0.000 abstract description 26
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000008685 targeting Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000013528 metallic particle Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910008045 Si-Si Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910006411 Si—Si Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a kind of solar battery and preparation method thereof and etching methods, technical solution of the present invention carries out making herbs into wool twice to silicon substrate, first time making herbs into wool forms the first groove in the first surface of silicon substrate, due to the targeting of the first groove, in second of making herbs into wool, it can be based on first groove, form the second groove, the second groove formed has multiple side walls, it can make incident ray that multiple reflections occur in the second groove in this way, to improve the absorption to light, reflectivity is reduced.
Description
Technical field
The present invention relates to technical field of solar batteries, more specifically, being related to a kind of solar battery and its production side
Method and etching method.
Background technique
With the continuous development of science and technology, more and more electronic equipments are widely used in people's daily life
In, huge convenience is brought for daily life and work, becomes the indispensable important tool of current people.Electricity
It can be the precondition for maintaining electronic equipment to work normally.With being constantly progressive for human society, various electronic equipments are to electric energy
Demand it is also increasing, power shortage caused by energy crisis is that current people have to face great difficult problem.
Solar battery can use solar power generation, be an important development direction for solving energy crisis.Making herbs into wool is
The first procedure for manufacturing crystal silicon solar energy battery forms light trapping structure in silicon chip surface, increases the utilization rate of light, is manufacture
One core link of solar battery.Good suede structure can not only reduce the reflectivity of sunlight, increase the suction of light
It receives, surface passivation effect and electrode contact performance can also be improved, to improve the collection efficiency of carrier.
In the prior art, alkali making herbs into wool processing generally is carried out to the light-receiving surface of cell substrate, being formed has multiple golden words
The flannelette of tower-shaped bulge-structure, to reduce the reflectivity of light-receiving surface.But the flannelette reflectivity of existing etching method preparation is still
It is higher.
Summary of the invention
In view of this, technical solution of the present invention provides a kind of solar battery and preparation method thereof and etching method,
Surface of silicon is handled by making herbs into wool twice, forms the flannelette with multiple second grooves, and the second groove has multiple side walls, can
So that in the second groove multiple reflections occur for incident ray, to improve the absorption to light, reflectivity is reduced.
To achieve the goals above, the invention provides the following technical scheme:
A kind of etching method, the etching method include:
One silicon substrate is provided, there is first surface；
First time making herbs into wool is carried out to the first surface, forms multiple first grooves in the first surface；
Second of making herbs into wool is carried out to the first surface, is based on first groove, forms the second groove, described second is recessed
Slot has multiple side walls.
Preferably, described to include: to first surface progress first time making herbs into wool in above-mentioned etching method
In the first surface deposited metal simple substance particle；
The first surface is immersed in the first reagent, by electrochemical reaction, so that the metal simple-substance particle exists
The first surface sinks；
The metal simple-substance particle is removed, first groove is formed.
Preferably, described to include: in the first surface deposited metal simple substance particle in above-mentioned etching method
It is reacted using the second reagent with the silicon substrate, forms the metal simple-substance particle in the first surface；
Wherein, second reagent includes AgNO3、H2O2And HF, the metal simple-substance particle are Ag particle.
Preferably, in above-mentioned etching method, first reagent includes H2O2And HF；
Submerging the duration is 120s-180s, including endpoint value.
Preferably, in above-mentioned etching method, the removal metal simple-substance particle includes:
The first surface is immersed in third reagent, the anti-of the metal simple-substance particle and the third reagent is passed through
The metal simple-substance particle should be removed.
Preferably, in above-mentioned etching method, further includes:
Before carrying out second of making herbs into wool, expand the aperture of first groove.
Preferably, in above-mentioned etching method, the aperture for expanding first groove includes:
The first surface is immersed in the 4th reagent, so that the silicon of first groove location and the 4th examination
Agent reaction, to expand the aperture of first groove.
Preferably, in above-mentioned etching method, second groove be pyramid connected in star, it is described to the first surface into
Second of making herbs into wool of row includes:
Reactive ion etching is carried out to the first surface, anisotropic etching is carried out to first groove, forms institute
State the second groove.
The present invention also provides a kind of production methods of solar battery, comprising:
Using etching method as described in any one of the above embodiments, making herbs into wool is carried out to silicon substrate.
The present invention also provides a kind of solar battery prepared using above-mentioned production method, the solar battery packets
It includes:
The first surface of silicon substrate, the silicon substrate forms multiple grooves by process for etching, and the groove has multiple
Side wall.As can be seen from the above description, in solar battery that technical solution of the present invention provides and preparation method thereof and etching method,
Making herbs into wool twice is carried out to silicon substrate, first time making herbs into wool forms the first groove in the first surface of silicon substrate, due to the first groove
Targeting can be based on first groove in second of making herbs into wool, form the second groove, the second groove tool of formation
There are multiple side walls, can make incident ray that multiple reflections occur in the second groove in this way, so that the absorption to light is improved, drop
Antiradar reflectivity.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the schematic illustration that the suede structure with pyramid protrusion reduces reflectivity；
Fig. 2 is the schematic illustration that the suede structure with inverted pyramid groove reduces reflectivity；
Fig. 3 is a kind of method flow diagram of etching method provided in an embodiment of the present invention；
Fig. 4 is a kind of method flow diagram of first time making herbs into wool provided in an embodiment of the present invention；
Fig. 5 is a kind of schematic illustration of deposited metal simple substance particle provided in an embodiment of the present invention；
Fig. 6 is the sinking schematic illustration of metal simple-substance particle in etching method described in the embodiment of the present invention；
Fig. 7 is a kind of schematic illustration of second of making herbs into wool provided in an embodiment of the present invention；
Fig. 8 is the SEM figure for the suede structure that etching method described in the embodiment of the present invention is formed；
Fig. 9 is the reflectivity contrast curve chart of the suede structure that the embodiment of the present invention is formed and traditional suede structure.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
As stated in the background art, existing etching method is alkali etching method, and being formed in silicon chip surface has pyramid convex
The suede structure risen, can be with reflectivity 11.5% or so.As shown in FIG. 1, FIG. 1 is the suede structure drops with pyramid protrusion
The schematic illustration of antiradar reflectivity a, side of light (in Fig. 1 shown in arrow) one pyramid protrusion of incidence, at most can be anti-
It is incident upon the one side of another pyramid protrusion, Ray Of Light can carry out respectively in the opposite two sidewalls of two pyramid protrusions
Reflection, and each pyramid protrusion is only capable of reflecting same Ray Of Light primary, reflectivity still to be improved to the absorption of light
It is higher.
The suede structure with inverted pyramid groove is formed in light-receiving surface, relative to the suede structure with pyramid protrusion
Reflectivity can be further decreased.After Ray Of Light incidence inverted pyramid groove, can between multiple side walls of groove into
Row multiple reflections reduce reflectivity to improve the absorption to light.As shown in Fig. 2, Fig. 2 is with inverted pyramid groove
Suede structure reduces the schematic illustration of reflectivity, and an inverted pyramid groove is shown in Fig. 2, and inverted pyramid groove is pyramid
Connected in star can make incident ray (in Fig. 2 shown in arrow) in inverted pyramid since inverted pyramid groove has multiple side walls
Multiple reflections occur in groove, that is to say, that its different side can be passed through in an inverted pyramid groove with Ray Of Light
Wall carries out multiple reflections.
As it can be seen that multiple reflections can be carried out between an inverted pyramid groove different lateral with Ray Of Light, and then have
There is multiple absorption process, relative to the suede structure with pyramid protrusion, the suede structure with inverted pyramid groove can be with
The absorption to light is improved, reflectivity is substantially reduced.
But it is by raw in silicon substrate surface that conventional preparation at present, which has the method for the suede structure of inverted pyramid groove,
At polymer microballoon single thin film, substrate-polymer microballoon single thin film is obtained；In the substrate-polymer microballoon single thin layer
Mask layer is generated on film, obtains substrate-polymer microballoon single thin film-mask layer；Remove the substrate-polymer microballoon single layer
Polymer microballoon in film-mask layer makes surface exposure go out multiple units of non-mask film covering；Corrosion does not cover the exposure mask
Unit be inverted pyramid connected in star, obtain inverted pyramid array structure flannelette.This method complex process and equipment precision is wanted
It asks high, is unfavorable for pushing mass production to.
To solve the above-mentioned problems, the embodiment of the invention provides a kind of solar battery and preparation method thereof and making herbs into wool sides
Method carries out making herbs into wool twice to silicon substrate, and first time making herbs into wool forms the first groove in the first surface of silicon substrate, due to the first groove
Targeting, in second of making herbs into wool, can be based on first groove, formed the second groove, the second groove of formation
With multiple side walls, manufacture craft is simple, low manufacture cost, and can substantially reduce reflectivity.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
With reference to Fig. 3, Fig. 3 is a kind of method flow diagram of etching method provided in an embodiment of the present invention, the etching method packet
It includes:
Step S11: providing a silicon substrate, has first surface.
The silicon substrate can be monocrystalline substrate or multicrystalline silicon substrate.It can according to demand, by monocrystalline prescribed slice
The monocrystalline silicon piece for forming pre-set dimension, as the silicon substrate.The demand size of silicon substrate can be sliced preparation according to demand, this
Inventive embodiments are not specifically limited in this embodiment, such as can be 156.75mm*156.75mm.
Step S12: first time making herbs into wool is carried out to the first surface, forms multiple first grooves in the first surface.
Step S13: second of making herbs into wool is carried out to the first surface, is based on first groove, forms the second groove, institute
The second groove is stated with multiple side walls.
Traditional process for etching is only through a making herbs into wool process, to the whole of silicon substrate when surface of silicon forms groove
A surface performs etching, and the lattice attribute based on silicon crystal forms the groove of specific shape in surface of silicon.But due to system
Suede process is directed to same entire surface and carries out, and without direction action, the lattice attribute based on silicon crystal forms a depthkeeping
After spending groove, even if persistently performing etching again, part outside groove and interior part can synchronize be removed, can not further increase
Big groove depth.And in etching method described in the embodiment of the present invention, after forming the first groove by first time making herbs into wool, also to silicon
Substrate carries out second of making herbs into wool, and the second groove is formed on the basis of the first groove, and the first groove has targeting, thus
The first groove is etched again in second of etching process, increase groove size, the extension including depth of groove and width,
Increase inside grooves surface area, the second groove of formation has multiple side walls, increases light absorption, reduces reflectivity.
In the etching method, the suede structure of formation can greatly increase the absorption of light, and increase thinks utilization rate to light,
Reflectivity can be reduced to 8% or so, when being used to prepare solar battery, and solar battery has better short circuit current, can
To improve the transfer efficiency of solar battery.
In the embodiment of the present invention, the second groove of formation can be inverted pyramid groove, as cold conical socket, generally,
Lattice attribute based on silicon crystal, formation be rectangular pyramid shape groove.First time making herbs into wool uses MCCE (Metal
Catalyzed Chemical Etching, metal catalytic chemical attack), second of making herbs into wool uses RIE (Reactive Ion
Etching, reactive ion etching).After completing first time making herbs into wool and second of making herbs into wool, the alkaline reagent pair of low concentration can be passed through
First surface is modified, to form the suede structure of the good inverted pyramid array of pattern.
In the embodiment of the present invention, described method such as Fig. 4, Fig. 4 that first time making herbs into wool is carried out to the first surface is this hair
A kind of method flow diagram for first time making herbs into wool that bright embodiment provides, this method comprises:
Step S21: in the first surface deposited metal simple substance particle.
In the step, it is described the first surface deposited metal simple substance particle include: as shown in figure 5, Fig. 5 for the present invention
A kind of schematic illustration for deposited metal simple substance particle that embodiment provides, it is anti-using the second reagent 12 and the silicon substrate 11
It answers, forms SiO in first surface S12Film layer and metal simple-substance particle 13；Wherein, second reagent 12 includes AgNO3、
H2O2And HF, second reagent 12 are AgNO3、H2O2And the aqueous solution (aq) of HF.The metal simple-substance particle is Ag
Grain.Silicon substrate 11 is in AgNO3+H2O2In+HF system, Ag-It can be reacted with Si, Ag-Oxidisability is stronger, can be from Si-Si bond
Obtaining electronics becomes simple substance Ag, and the Ag metallic particles of generation is attached to first surface S1 at random.
In Fig. 5, left figure indicates silicon substrate 11 in AgNO3+H2O2In+HF reaction system, middle graph indicates Ag-From Si-Si bond
Middle acquisition electronics becomes simple substance Ag particle, and right figure indicates that Ag particle is attached to first surface S1 at random.
Step S22: the first surface is immersed in the first reagent, by electrochemical reaction, so that the metal list
Matter particle sinks in the first surface.
In the step, first reagent includes H2O2And HF；Submerge the duration be 120s-180s, such as persistently when
Between can be 150s.Including endpoint value.As shown in fig. 6, Fig. 6 is metal simple-substance particle in etching method described in the embodiment of the present invention
Sinking schematic illustration, in the first reagent, as cathode, Si is constituted as anode in first surface S1 Ag metallic particles
Micro- electrochemical reaction channel, H2O2Si is oxidized to SiO2, HF is by the SiO below Ag metallic particles2It washes, forms etching hole,
So that Ag metallic particles sinks, 150s is persistently submerged in this way, after reacting 150s, is formed the poroid suede structure of nanometer, is then used
Deionized water cleaning, can such as clean 180s.In Fig. 6, left figure indicates the SiO below Ag particle2It is removed, right figure indicates Ag
Grain sinks.
Step S23: removing the metal simple-substance particle, forms first groove.
In the step, the removal metal simple-substance particle includes: that the first surface is immersed in third reagent,
The metal simple-substance particle is removed with reacting for the third reagent by the metal simple-substance particle, forms the second groove, the
Two grooves are nano-pore.Third reagent can be nitric acid, reaction time 300s, and then the metal simple-substance in removal carbon nano-pore
Particle.Then 180s is cleaned with deionized water.
In etching method described in the embodiment of the present invention, further includes: before carrying out second of making herbs into wool, expand first groove
Aperture.The aperture for expanding first groove includes: that the first surface is immersed in the 4th reagent, so that institute
The silicon for stating the first groove location is reacted with the 4th reagent, to expand the aperture of first groove.4th reagent can be
HF and HNO3Mixed solution, the reaction time can be 180s, nanometer bore dia is empty big, then be cleaned with deionized water
180s。
In the embodiment of the present invention, second groove is pyramid connected in star, described to carry out second to the first surface
Making herbs into wool includes: to carry out reactive ion etching to the first surface, carries out anisotropic etching to first groove, forms institute
State the second groove.
Reactive ion etching is based on physical sputtering and to have the process of chemical reaction concurrently.It is realized by physical sputtering longitudinal
Etching, while applied chemistry is reacted to reach required selection ratio, to control fidelity well.Reactive ion etching
In the process, etching gas (the mainly gas of F base and CL base) produces under high-frequency electric field (frequency is usually 13.56MHz) effect
Raw glow discharge, ionizes gas molecule or atom, is formed plasma (Plasma).In the plasma, include
Cation (Ion+), anion (Ion-), free radical (Radical) and free electron (e).Free radical is wave very living in chemistry
, it is chemically reacted with the material (silicon materials of silicon substrate as described in the embodiments of the present invention) being etched, and generation can be by
The volatile compound that air-flow is taken away, to realize chemical etching.
The principle of second of making herbs into wool is as shown in fig. 7, Fig. 7 is a kind of principle of second of making herbs into wool provided in an embodiment of the present invention
Schematic diagram, during reactive ion etching, silicon substrate is placed in cathode, is oppositely arranged with anode, caused by radio-frequency power supply RF
Electronegative free electron reaches cathode because quality is small, movement velocity is fast quickly under the action of electric field；And cation is then due to matter
Amount is big, and speed interior at the same time cannot reach cathode slowly, so that cathode be made to be formed about electronegative plasma arc voltage.Together
When since the operating air pressure of reaction chamber is 10-3Torr-10-2Torr, such cation obtain very effective add near cathode
Speed, vertical bombardment are placed in the silicon substrate of cathode surface, and this ion bombardment can greatly speed up the chemical reaction and reaction on surface
The desorption of product, so as to cause very high etch rate.Presence just because of ion bombardment just makes anisotropic etching
It is achieved.
In etching method described in the embodiment of the present invention, the first groove is formed by first time making herbs into wool first, the first groove is
Nano-pore, then by second of making herbs into wool, the inner wall for nano-pore exposes silicon crystal in silicon substrate, can based on the first groove
To carry out further anisotropic format to the first groove, the lattice attribute based on silicon crystal forms the second groove, so that the
Two grooves are pyramid connected in star, due to being initially formed the first groove, can be made during second of making herbs into wool in the first groove
The opposite part having outside the first groove in part be easier to etch, so as to form larger sized second groove.
After completing second of making herbs into wool, silicon substrate is placed in 1.25 ‰ KOH solution and cleans 30s, cleaned with deionized water
120s, then volume fraction be 10% HF and volume fraction be 10% HCl mixed solution in clean 120s, finally dry,
It is finally completed the making herbs into wool process to silicon substrate.
As shown in figure 8, Fig. 8 is the SEM figure for the suede structure that etching method described in the embodiment of the present invention is formed, it is seen then that logical
The second groove of formation for crossing etching method described in the embodiment of the present invention is pyramid shape groove structure.
As shown in figure 9, the reflectivity comparison song of suede structure and traditional suede structure that Fig. 9 is formed for the embodiment of the present invention
Line chart, what etching method of the embodiment of the present invention was formed is the groove of specific inverted pyramid shape, and reflectivity 8.8%, make by tradition
The positive pyramid structure that velvet figures method is formed, reflectivity 11.5%, it is seen that etching method described in the embodiment of the present invention, it can be effective
Reduce reflectivity.
Etching method described in the embodiment of the present invention can carry out a making herbs into wool to silicon substrate using MCCE and RIE respectively
Process, simple process and low cost.And the lower suede structure of reflectivity can be formed in surface of silicon.Using the present invention
The reflectivity for the suede structure that etching method described in embodiment is formed can greatly improve light absorption in 8%-9%, improve photoelectricity
Transfer efficiency.
Based on the above embodiment, another embodiment of the present invention additionally provides a kind of production method of solar battery, the system
It include: that making herbs into wool is carried out to silicon substrate using etching method described in above-described embodiment as method.Other technical process, such as diffusion,
Passivation and electrode preparation etc., same as the prior art, details are not described herein.
Based on the above embodiment, another embodiment of the present invention additionally provides a kind of solar battery, which is characterized in that described
Solar battery includes: silicon substrate, and the first surface of the silicon substrate forms multiple grooves, the groove tool by process for etching
There are multiple side walls.
The solar battery production method preparation through the foregoing embodiment, process for etching is simple, low manufacture cost,
And the suede structure of antiradar reflectivity can be formed, photoelectric conversion efficiency with higher.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For the sun disclosed in embodiment
Can for battery and preparation method thereof, since it is corresponding with etching method disclosed in embodiment, so be described relatively simple,
Related place illustrates referring to etching method corresponding part.
It should also be noted that, herein, relational terms such as first and second and the like are used merely to one
Entity or operation are distinguished with another entity or operation, without necessarily requiring or implying between these entities or operation
There are any actual relationship or orders.Moreover, the terms "include", "comprise" or its any other variant are intended to contain
Lid non-exclusive inclusion, so that article or equipment including a series of elements not only include those elements, but also
It including other elements that are not explicitly listed, or further include for this article or the intrinsic element of equipment.Do not having
In the case where more limitations, the element that is limited by sentence "including a ...", it is not excluded that in the article including above-mentioned element
Or there is also other identical elements in equipment.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of etching method, which is characterized in that the etching method includes:
One silicon substrate is provided, there is first surface；
First time making herbs into wool is carried out to the first surface, forms multiple first grooves in the first surface；
Second of making herbs into wool is carried out to the first surface, is based on first groove, forms the second groove, the second groove tool
There are multiple side walls.
2. etching method according to claim 1, which is characterized in that described to carry out first time making herbs into wool to the first surface
Include:
In the first surface deposited metal simple substance particle；
The first surface is immersed in the first reagent, by electrochemical reaction, so that the metal simple-substance particle is described
First surface sinks；
The metal simple-substance particle is removed, first groove is formed.
3. etching method according to claim 2, which is characterized in that described in the first surface deposited metal simple substance
Grain include:
It is reacted using the second reagent with the silicon substrate, forms the metal simple-substance particle in the first surface；
Wherein, second reagent includes AgNO3、H2O2And HF, the metal simple-substance particle are Ag particle.
4. etching method according to claim 2, which is characterized in that first reagent includes H2O2And HF；
Submerging the duration is 120s-180s, including endpoint value.
5. etching method according to claim 2, which is characterized in that the removal metal simple-substance particle includes:
The first surface is immersed in third reagent, reacting for the metal simple-substance particle and the third reagent is passed through
Except the metal simple-substance particle.
6. etching method according to claim 1, which is characterized in that further include:
Before carrying out second of making herbs into wool, expand the aperture of first groove.
7. etching method according to claim 6, which is characterized in that the aperture for expanding first groove includes:
The first surface is immersed in the 4th reagent, so that the silicon of first groove location and the 4th reagent are anti-
It answers, to expand the aperture of first groove.
8. etching method according to claim 1-7, which is characterized in that second groove is that pyramid is recessed
Slot, it is described to include: to the first surface second of making herbs into wool of progress
Reactive ion etching is carried out to the first surface, anisotropic etching is carried out to first groove, forms described the
Two grooves.
9. a kind of production method of solar battery characterized by comprising
Using such as described in any item etching methods of claim 1-8, making herbs into wool is carried out to silicon substrate.
10. a kind of solar battery prepared using production method as claimed in claim 9, which is characterized in that the solar energy
Battery includes:
The first surface of silicon substrate, the silicon substrate forms multiple grooves by process for etching, and the groove has multiple side walls.
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| CN112349738A (en) * | 2020-10-27 | 2021-02-09 | 武汉新芯集成电路制造有限公司 | Semiconductor device, forming method thereof and image sensor |
| CN112349739A (en) * | 2020-10-27 | 2021-02-09 | 武汉新芯集成电路制造有限公司 | Semiconductor device, forming method thereof and image sensor |
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| CN114420774A (en) * | 2021-11-29 | 2022-04-29 | 江苏科来材料科技有限公司 | Texturing process of crystalline silicon battery |
| CN117059681A (en) * | 2023-10-09 | 2023-11-14 | 晶科能源(海宁)有限公司 | Solar cell, manufacturing method thereof and photovoltaic module |
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