CN103849937B - The surface treatment method of substrate used for solar batteries - Google Patents
The surface treatment method of substrate used for solar batteries Download PDFInfo
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- CN103849937B CN103849937B CN201310488489.7A CN201310488489A CN103849937B CN 103849937 B CN103849937 B CN 103849937B CN 201310488489 A CN201310488489 A CN 201310488489A CN 103849937 B CN103849937 B CN 103849937B
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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
- H01L31/04—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
- 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 relates to the surface treatment method of a kind of substrate used for solar batteries.According to the surface treatment method of the present invention, the first Wet-type etching operation, reactive ion etching work procedure and the second Wet-type etching operation are carried out for substrate used for solar batteries, to form pyramid structure on the surface of the substrate.This pyramid structure reduces light reflectivity, to improve the efficiency of light absorption of solar cell.In accordance with the invention it is possible to do not limited by the kind crystallized and directionality, and effectively class monocrystal substrate is carried out surface process, thus improve the efficiency of solar cell.
Description
Technical field
The present invention relates to the surface treatment method of a kind of substrate used for solar batteries.More particularly, to one
Plant and can not be limited by the kind of the trellis of substrate or quality and effectively carry out surface structuration
The surface treatment method of substrate used for solar batteries.
Background technology
In recent years, it is contemplated that the exhaustion of the existing energy such as oil or coal, replacing of these energy will be substituted
Increasingly receive publicity for the energy.Wherein, solar cell utilizes as one and is directly changed by solar energy
For the battery of future generation of the semiconductor element of electric energy, attracted attention by people.Solar cell is divided into silicon solar electricity
Pond (silicon solar cell), compound semiconductor solar cell (compound semiconductor
Solar cell) and laminated solar battery (tandem solar cell) these several big types.
On the other hand, the silicon class solar cell as major part solar cell of batch production now,
Use silicon is as semiconductor substrate, and silicon is as indirect interband band-gap semiconductor (indirect interband
Transition semiconductor), electronics could be produced owing to only having the light of the band-gap energy more than silicon
-hole pair, so the absorptivity of light is on the low side.Therefore, silicon class solar cell makes to inject in solar cell
The light of more than the 30% of portion reflects from the silicon wafer surface as substrate, and therefore the efficiency of solar cell will
Reduce.
In order to reduce this optical loss, surface is used to process (texturing) in silicon solar cell
Method.Surface treatment method is in order to make most luminous energy be inhaled into inside wafer substrate, at silicon solar electricity
Formed concavo-convex on the silicon substrate in pond, to improve surface roughness.Beginning light arrives and collides and inclines
On oblique pyramid wall, a part is absorbed, and a part reflects back, and now, makes the light of return
Continue to collide on other gold tower walls, to increase absorbing amount.So, Pyramid structure increases light
Uptake, result can improve battery efficiency.Therefore, if manufacturing silicon solar by surface treatment method
Cell substrates, it becomes possible to realize the minimizing of surface reflection of solar cell, the carrying of carrier collection effect
Height and the light binding effect by the internal reflection of solar cell.
As surface treatment method, the wet type surface of the most useful acidity or alkaline solution processes and with anti-
The dry type surface answering ionized gas processes both modes.Wet type surface process in use alkaline solution or
Person's acid solution, alkaline solution is suitable for single-crystal wafer, and acid solution is suitable for the surface of polycrystalline wafers
Reason.And, dry type surface processes and uses reactive ion gas, and is suitable for polycrystalline wafers.
On the other hand, a kind of method that class monocrystal substrate is used for manufacturing solar cell is had to be in recently
Exploitation in the middle of, the method due to technique simply, once can manufacture in a large number and there is high price competitiveness.
For described class monocrystalline silicon, such as at US publication the 20100193031st, European patent
No. 0748884 grade discloses the method utilizing crystal seed (seed) to make class monocrystalline silicon growing.
Owing to class monocrystalline silicon is according to growing method, single-crystal region is all contained in polycrystalline together with, so very
Difficulty carries out surface process equably to all regions.Therefore, in order to class monocrystalline silicon is used for solar cell,
It is necessary that the light making substrate is absorbed the maximized surface treatment method of change studies.
Summary of the invention
For solving the problems referred to above, it is an object of the invention to provide a kind of for substrate used for solar batteries,
Particularly with class monocrystal substrate, do not limited by the kind crystallized and directionality and effectively carried out surface
The method of reason.
For reaching above-mentioned purpose, the present invention provides the surface treatment method of a kind of substrate used for solar batteries,
Comprise the following steps: the first Wet-type etching is carried out for substrate used for solar batteries；Carry out reactive ion
Etching (reactive ion etching)；And carry out the second Wet-type etching.
In accordance with the invention it is possible to substrate used for solar batteries to be carried out effectively surface process, thus reduce
Reflectance, increases absorptivity, and then manufactures high efficiency solar cell.
And, not by being divided into the kind of different types of class monocrystal substrate to be limited according to crystallinity, and only
Just can carry out surface process equably by a kind of method, therefore, it is possible to Simplified flowsheet, reduce expense.
Accompanying drawing explanation
Fig. 1 is for electron microscope, carrying out the process of wet type surface for monocrystal substrate and polycrystalline substrate
Result amplifies the photo of 5000 times of shootings.
Fig. 2 is the figure of the substrate showing multiple quality.
Fig. 3 is for microscope, carrying out surface with alkaline solution and acid solution to class monocrystal substrate respectively
The photo of the result bust shot processed.
Fig. 4 will be for by SEM, will proceed to reactive ion etching work in described embodiment 1
The photo of 70000 times of shootings is amplified on the surface of the substrate after sequence.
Fig. 5 will be for by SEM, will proceed to reactive ion etching work in described embodiment 1
The photo of 5000 times of shootings is amplified on the surface of the substrate after sequence and the second Wet-type etching operation.
Fig. 6 is the reflectance of the substrate before display carries out surface process and in described embodiment 1 with compare
Example 1 carries out the chart of the reflectance of substrate after process of surface treatment.
Detailed description of the invention
The surface treatment method of the present invention, comprises the following steps:
First Wet-type etching is carried out for substrate used for solar batteries；
Carry out reactive ion etching (reactive ion etching)；And
Carry out the second Wet-type etching.
With first, second term such as grade, various structural elements, the use mesh of described term are described in the present invention
Be only that one structural element of differentiation and other structural elements.
And, the term used in this manual is simply to illustrate that exemplary embodiments, and it is intended to not
It is to limit the present invention.The statement of odd number unless there is the most different meanings within a context, then includes multiple
Number.In this manual, " include ", the term such as " having " or " having " is intended to specify the spy implemented
Levy, numeral, step, structural element or the existence of these factor combinations, should not be construed as getting rid of in advance
One or other features more than one or numeral, step, structural element or these factor combinations
Existence or additional possibility.
And, in the present invention, when relate to each layer or key element be formed at each layer or key element it " on "
Or time " above ", represent that each layer or key element are formed directly on each layer or key element, or table
Show that other layers or key element can be formed between each layer, on subject or base material further.
The present invention can carry out numerous variations, can have variform, specific embodiment is illustrated below, go forward side by side
Row describes in detail.But this is not intended to limit the invention to disclosed specific modality and provide,
But it is understood to include all changes, equivalent and the replacement in the thought of the present invention and technical scope
Thing.
Below, the surface treatment method of the substrate used for solar batteries that present invention will be described in detail with reference to the accompanying.
Substrate required in semiconductor used for solar batteries is according to the technology used when purity, prepared substrate
Precision etc., in quality with there is the biggest difference in price.Required essential condition has the concentration making impurity
The high-purity minimized, the high-quality making crystal defect minimize and the low price etc. that can produce in batches,
These conditions are the most important parts of the batch production determining solar cell.According to this trend,
The substrate of nearly exploitation has the class monocrystal substrate (mono-like with monocrystalline and polycrystalline both forms
Multi wafer, MLM wafer).
Class monocrystal substrate combines the advantage of monocrystalline and polycrystalline, utilizes polycrystalline ingot growth method etc. to produce.
Prepared by the heat exchange method (HEM Heat Exchange Method) that can use one of conventional polycrystalline ingot growth method
Single crystal rod, and be used for producing high efficiency solar cell.Polycrystalline ingot growth method is simple due to technique, and one
Secondary can produce in a large number, therefore there is the characteristic that price competitiveness is high, recently in order to as solar energy
Battery substrate and be in exploitation in the middle of.
On the other hand, absorb to improve the light of solar cell, substrate surface is carried out making herbs into wool process
(texturing, also referred to as " surface texturing mechanism " or " surface process ") operation.If processing system by making herbs into wool
Make solar cell substrate, can be achieved with the minimizing of surface reflection of solar cell, carrier collection effect
Raising really and the light binding effect by the internal reflection of solar cell.
Monocrystal substrate refers to that entirety has the substrate of the single crystallization of consistent crystal orientation, for described list
Brilliant substrate, with alkaline solutions such as NaOH or KOH, carries out making herbs into wool (texturing) to substrate surface
Anisotropic etching be effective.
On the contrary, polycrystalline substrate refers to the crystallization of multiple random orientation crystalline substrate in the main body of substrate,
For described polycrystalline substrate, because crystallization direction is different, the isotropic etching Billy of acid solution is utilized to use
The etching of alkali is more effective.
Fig. 1 will be for by SEM, carrying out the process of wet type surface to monocrystal substrate and polycrystalline substrate
Result amplify 5000 times shooting photos.
In FIG, left photo is that monocrystal substrate carries out the photo of wet type surface process with alkaline solution,
Right photograph is that polycrystalline substrate carries out the photo of wet type surface process with acid solution.With reference to Fig. 1, single
Brilliant substrate and polycrystalline substrate are according to the feature crystallized, and respective form is different, but shows in single substrate
Uniform etch morphology.
But, class monocrystal substrate is divided into the substrate of 100% monocrystalline, single-crystal region according to growing method and condition
The substrate mixed with polycrystalline and the substrate of 100% polycrystalline, generally by single-crystal region and polycrystalline
In district is all contained in, therefore it is difficult to all of region is carried out equably surface process.
Fig. 2 is for showing the figure of the substrate of multiple quality (grade).
Understand with reference to Fig. 2, be from left to right 100% monocrystal substrate (Mono wafer), single-crystal region and many
Class monocrystal substrate (MLM wafer grade A, B) that crystalline region mixes and 100% polycrystalline substrate
The substrate of multiple qualities such as (Multi wafer).
In general, class monocrystal substrate can be divided into three kinds of ranks according to the ratio shared by monocrystalline (mono) district,
I.e. the ratio shared by single-crystal region be more than 90% for A level, more than 70% for B level, more than 25%
For C level.
In general, the class monocrystal substrate of A level, almost identical with single-crystal wafer, therefore can be molten by alkalescence
Liquid is etched.But less than the substrate of A level, i.e. the substrate of B level or C level is many owing to comprising respectively
Therefore individual single-crystal region and polycrystalline, when processing with alkalescence or acid solution, it is difficult to realize optimal making herbs into wool.
Fig. 3 is for will carry out surface with alkaline solution and acid solution to class monocrystal substrate respectively with microscope
The photo of the result bust shot of reason.In figure 3, left photo is to class monocrystal substrate with alkaline solution
Carrying out the photo of surface process, right photograph is, with acid solution, class monocrystal substrate is carried out surface process
Photo.
As class monocrystal substrate carried out surface texturing mechanism, then due to the crystallization direction of single-crystal region with alkaline solution
Identical, therefore, it is possible to etch the micro-pyramid structure with antiradar reflectivity, but polycrystalline is due to crystallization
Direction is different, thus it is shown that the etch morphology different from monocrystalline.Uneven because of this monocrystalline and polycrystalline
Surface texturing mechanism, such as the left photo of Fig. 3, it can be seen that occur as the maple leaf phenomenon of maple leaf shape.By
The reason reducing commodity value can be become in this phenomenon, be therefore not suitable for.
On the contrary, when carrying out surface texturing mechanism with acid solution, do not limited by crystallization direction and with identical
Etching speed forms randomly shaped gold tower (random pyramid), therefore such as the right photograph of Fig. 3,
And occur without maple leaf shape (maple-shape).But, carry out surface texturing mechanism by acid solution
Substrate, than being carried out the substrate of surface texturing mechanism by alkaline solution, shows higher reflectance.Therefore lead to
The surface texturing mechanism of peracidity solution is the most improper.
Surface treatment method according to the present invention, it is possible to not by the single-crystal region of substrate surface or polycrystalline etc.
The restriction of lattice structure and carry out surface texturing mechanism.Therefore, it is possible to realize uniform surface texturing mechanism, and energy
According to lattice structure, enough solution shows that the phenomenon of different surface texturing mechanism i.e. produces maple leaf shape
(maple-shape) problem, and it is possible to prevent because of the product of maple leaf shape (maple-shape)
Give birth to and cause the reduction of commodity value.It is additionally, since processing step simple, therefore has and can reduce work
Skill time and the advantage of expense.
According to the surface treatment method of the present invention, the substrate used for solar batteries processing object as surface can
For class monocrystal substrate.As it has been described above, described class monocrystal substrate can be monocrystal substrate, single-crystal region and polycrystalline
The substrate mixed or polycrystalline substrate, and can be the substrate of multiple rank.Table according to the present invention
Face processing method, it is possible to do not limited by kind or the rank of substrate and be applicable in technique.Therefore,
Even if using the rudimentary substrate that price is relatively low, the table being equivalent to use the substrate of senior rank also can be obtained
Face result, therefore, it is possible to substantially reduce producing cost.
According to one embodiment of the invention, described substrate used for solar batteries can be such as by p-type conductivity
Silicon constitute substrate.When described substrate used for solar batteries has p-type electric-conducting type, containing boron (B),
The triad impurity such as gallium or indium.
Or, described substrate used for solar batteries can be by the substrate constituted such as the silicon of n-type conductivity type.
When described positive substrate used for solar batteries has N-shaped conduction type, can contain phosphorus (P), arsenic (As),
The pentad impurity such as antimony (Sb).
To above-mentioned substrate used for solar batteries, first carry out the first Wet-type etching (wet etching).
By described first Wet-type etching, it is possible to realize removing cutting damage (sawing damage simultaneously
Removal) and the first making herbs into wool (texturing).Described removal cutting damage is to remove because of the cutting of substrate
The defect produced, and remove the operation forming oxide-film from the teeth outwards.
According to one embodiment of the invention, described first Wet-type etching uses acid (acid) solution.
More specifically, the acid solution used in described first Wet-type etching operation comprises HF, HNO3And
H2O, volume ratio is about 1:2～4:1～3, it is preferable that be about 1:3:2.
And, when carrying out described first Wet-type etching, can under conditions of temperature is about 5～10 DEG C,
Described solution impregnates substrate about 1～5 minute, preferably impregnates about 1～2 minute.
According to one embodiment of the invention, after carrying out above-mentioned first Wet-type etching operation, can make further
Carry out cleaning (rinse) for the first time by deionized water (DI water), carry out with alkaline solutions such as KOH
Neutralization step, with deionized water (DI water) carry out second time clean and HF clean, and spend from
Sub-water (DI water) carries out third time matting.
By carrying out above-mentioned first Wet-type etching, it is possible to remove the cutting damage of substrate, and by the
Form height on the substrate surface once etched and be about 2～10 μm, the concaveconvex structure of preferably about 3～5 μm.
Then, reactive ion etching is carried out for completing the substrate of described first Wet-type etching operation
(reactive ion etching, RIE) operation.
Described reactive ion etching work procedure, can be by carrying out plasma to etching gas, and being allowed to activation is
Strong reactiveness, and make its surface with substrate collide and implement.Can make as described etching gas
Use F2、SF6、CF4Etc. fluorine-based gas, Cl2Deng chlorine system gas and O2More than the one or two kinds of in Deng.
According to one embodiment of the invention, in described reactive ion etching work procedure, in order to adjust etching shape
State, can comprise O in described etching gas2.By comprising O in described etching gas2, not by
The side of Ions Bombardment forms the oxide-film playing mask effect, and is being formed without by the bottom of Ions Bombardment
Film such that it is able to regulate etch morphology by the phenomenon only etching bottom.
According to one embodiment of the invention, Cl can be used2、SF6And O2Carry out as described etching gas
Etching work procedure.
More specifically, after configuring described substrate in the chamber, by etching gas injecting chamber.Then, right
The electric power of two the electrodes applying prescribed level being arranged between described substrate, thus between two electrodes
Space produce plasma based on described etching gas.The plasma generated have hyperergic from
By base (radical) and ion (ion).Accelerate the plasma so generated so that it is enter with the surface of substrate
Row collision.Thus, by physical impact and the combination of chemical reaction, can on the surface of described substrate shape
Become multiple concaveconvex structure.
In described reactive ion etching work procedure, collide than the ion of general plasma etching higher energy
On substrate, this is because formed more higher negative potential than earth electrode on electrode.
By above-mentioned reactive ion etching work procedure, described substrate surface is carried out the second making herbs into wool process, with
Pyramid structure is formed on the surface of described substrate.
Described pyramid structure reduces the light reflectivity of substrate surface, thus the light improving solar cell is inhaled
Produce effects rate.Described pyramid structure i.e. can be passed through by controlling the process conditions of reactive ion etching work procedure
Etching gas, pressure, temperature, electrode height or power, be formed as variform and size.
According to one embodiment of the invention, in described pyramid structure, depth-width ratio is about 0.75～1.1.
And, maintaining in the range of described ratio, can have height and the width of several nanometer extremely hundreds of nanometers.
Such as, described pyramidal width is about 100～300nm, is highly about 150～350nm.According to
The present invention, substep carries out above-mentioned first Wet-type etching operation and reactive ion etching work procedure such that it is able to no
Limited by the crystalline texture of substrate and formed uniform pyramid structure from the teeth outwards.Thereby, it is possible to subtract
Few light quantity from surface reflection, thus realize low reflectance.
However it is possible to the surface caused because of the impact of the plasma of described reactive ion etching work procedure can be produced
Damage.If not removing surface damage, because of the raising of surface recombination velocity, current value can reduce, thus
It is difficult to expect the increase of battery conversion efficiency.That is, by reactive ion etching work procedure, reflectance step-down,
And then can increase light absorption, but due to the surface damage meanwhile produced, the disappearance of electron-hole pair is also
Can accelerate, therefore can not obtain and increase the effect that light absorbs.This can become the reason of low Voc and FF.
And, if maintaining to be excessively sharp by the pyramid structure of described reactive ion etching work procedure generation
(needle), then there is high electric leakage (leakage current) in pyramidal upper layer part branch.
Therefore, in order to maintain low reflectance and remove electrical surfaces's damage, work is etched at described reactive ion
After sequence, implement to remove surface damage (damage removal etching, DRE) operation.
Described removal surface damage operation is to remove the surface produced in reactive ion etching work procedure
Damage, if but carry out described removal surface damage operation too much, then can etch surface too much, enter
And remove the pyramid formed by reactive ion etching work procedure, thus low reflectance can not be obtained.Therefore,
Described removal surface damage operation is necessary be able to maintain that the golden word formed by reactive ion etching work procedure
Remove while tower structure and pass through O2Under the oxide-film produced and the optimum condition effectively removing surface damage
Carry out.
According to the surface treatment method of the present invention, carry out the second wet type as described removal surface damage operation
Etching work procedure.More specifically, described second Wet-type etching operation uses and comprises volume ratio and be about 1:13～17:
15～19, HF, HNO of preferably 1:15:173And H2The acid solution of O is carried out.By with above-mentioned
Condition is removed surface damage operation, it is possible under conditions of surface is not too much etched, and has both maintained logical
Cross the pyramid structure that reactive ion etching work procedure is formed, and maintain the depth-width ratio of described pyramid structure,
And make the top section of pyramid structure become soft (smoothly), thus improve reflectance, and prevent
Produce electric leakage.And, in the formation process of follow-up anti-reflective film, it is possible to effectively carry out antireflection
The deposition (deposition) of film, and by being obtained in that reflectance improves further with this synergy
Effect.According to one embodiment of the invention, by implementing described removal surface damage operation, it is possible to make
Reflectance ratio carries out the raising about 1～3% that takes a step forward of described removal surface damage operation.
Now, the technological temperature of the second Wet-type etching operation is normal temperature, such as, be about 20～30 DEG C, can
Impregnate about 10～60 seconds, preferably impregnate about 20～50 seconds.
According to one embodiment of the invention, described second Wet-type etching operation can be carried out as follows: logical
The etch quantity crossing described second Wet-type etching operation is to carry out the substrate before described second Wet-type etching operation
About the 0.009～0.035% of weight.
The substrate of surface process is carried out, it is possible to display about 9～12% with the surface treatment method of the invention described above
Surface reflectivity.
For the substrate through above-mentioned process of surface treatment, follow-up can be according to the general manufacturer of solar cell
Method, forms emitter layer, anti-reflective film, front electrode and backplate, thus obtain high efficiency too
Sun can battery.
More specifically, form emitter stage on the top of surface treated described substrate used for solar batteries
Layer.Can be adulterated in described emitter layer the impurity contrary with described substrate, to form P-N junction (P-N
Junction).According to one embodiment of the invention, described emitter layer is about the shallow of 100～500nm thickness
P-N junction emitter P-N layer, is applicable to high efficiency solar cell.
And, according to one embodiment of the invention, it is high that described emitter layer can have photoelectric transformation efficiency
Sheet resistance, e.g., from about 85～the sheet resistance of 100 Ω/sq.
Then, anti-reflective film is formed on the top of described emitter layer.
Described anti-reflective film can pass through vacuum deposition method, chemical vapour deposition technique, rotary coating, screen printing
Brush or spraying are formed, but are not so limited.And, described anti-reflective film can have and such as nitrogenizes
Silicon fiml, hydrogeneous silicon nitride film, silicon oxide film, silicon oxynitride film, MgF2、ZnS、TiO2And CeO2
In any one monofilm or combine the multi-layer film structure of plural film, but and so limited.Root
According to one embodiment of the invention, described anti-reflective film is the silicon nitride film of the refractive index with about 2.0～2.2,
It is formed as the thickness of about 75～85nm.
Then, after serigraphy silver (Ag) slurry, thermally processable formation front electrode, and at substrate
Back up aluminium paste after carry out being heat-treated and form backplate, thus manufacture solar cell.To described
Aluminium (Al) slurry is when being heat-treated, the aluminium back side diffusion by substrate such that it is able to overleaf electrode and
Back of the body electric field (Back Surface field) layer is formed in the boundary face of substrate.If forming back of the body electric field layer, then can
Enough prevent carrier from moving to the back side of substrate and carry out in conjunction with, if prevent carrier in conjunction with, then
Open-circuit voltage rises such that it is able to improve the efficiency of solar cell.
Below, with reference to embodiments of the invention, further describe the present invention.But these embodiments are only
But proposing for illustrating the present invention, the interest field of the present invention is not dependent on these and implements
Example.
<embodiment>
Embodiment 1
Prepare the p-type class monocrystal substrate (MLM wafer, Grade B) doped with iii group element impurity.
Comprising HF, HNO that volume ratio is 1:3:23And H2In the solution of O, it is 7 DEG C of conditions in temperature
Lower dipping substrate 1 point 30 seconds, to carry out the first Wet-type etching, thus is removed cutting damage simultaneously
Process with the first making herbs into wool.Processed by described first making herbs into wool, reach 3～5 μm from the etched thickness on surface.
Then, Cl is used as etching gas2/SF6/O2Implement reactive ion etching work procedure.By described
The pyramid structure that reactive ion etching work procedure generates, its height (Height) and width (width) it
It is distributed in the range of 0.75～1.1 than H/W.
Comprising HF, HNO that volume ratio is 1:15:173And H2In the solution of O, it it is 25 DEG C in temperature
Under conditions of impregnate substrate 30 seconds, to carry out the second Wet-type etching, after this etching, and carry out this
Comparing before etching, substrate weight reduces 0.025%, now completes surface and processes.
By using POCL3Diffusing procedure, Doping Phosphorus (P), formed have 85 Ω/sq resistance send out
Emitter layer.Formed on described emitter layer by PECVD device and there are 2.0～2.2 scope refractive indexes
Two-layer silicon nitride film, its gross thickness is 85nm.
Carry out serigraphy with Al paste overleaf, and be dried under the temperature conditions less than 200 DEG C
After operation, form front electrode with Ag paste with the width of 70 μm sizes, and in the temperature less than 200 DEG C
After being dried operation under the conditions of degree, enter in the belt firing furnaces of 940 DEG C (belt firing furnace)
Row sintering forms front electrode and backplate.
Comparative example 1
In addition to not carrying out reactive ion etching work procedure, with the method manufacture identical with described embodiment 1
Solar cell.
<experimental example>
The evaluation of surface result
Fig. 4 will be for by SEM, will carry out to reactive ion etching work in described embodiment 1
The photo of 70000 times of shootings is amplified on the surface of the substrate after sequence.
Fig. 5 will be for by SEM, will carry out to reactive ion etching work in described embodiment 1
The photo of 5000 times of shootings is amplified on the surface of the substrate after sequence and the second Wet-type etching operation.
Fig. 6 is the reflectance of the substrate before display carries out surface process and in described embodiment 1 with compare
Example 1 carries out the chart of the reflectance of substrate after process of surface treatment.
The electric property evaluation of solar cell
According to ASTM G-173-03, under AM1.5 illumination condition, use Korea Spro Hua Xinneng in China
The photovoltaic tester (solar tester) of source company (Hanwha Solarone limited, HSOL), i.e.
H.a.l.m cetis PV-products measures the solar-electricity manufactured in described embodiment 1 and comparative example 1
The electric property in pond, and the results are shown in table 1 below.In table 1 below, Isc represents when impedance is low,
By the maximum current transmitted corresponding to the solar cell of short circuit condition or when a solar cell
Both end voltage by 0 time the electric current that flow through, the electric current that per unit area is flow through is that Jsc, Voc are for working as
When electric current is 0, being formed at the voltage at solar cell two ends, expression can obtain from solar cell
Maximum voltage, parallel resistance Rsh refers to be connected in parallel the resistance of certain circuit, and low parallel resistance can cause
Electric leakage, thus reduce electric current and voltage.Series resistance Rs is at the upper and lower of solar cell electricity
The resistance worked by series connection (series) between pole, flows through this electricity by the electric current of emitter stage and base stage
Resistance, will be defined as Rs by vertical resistor composition, and the parameter that influence is big is FF.For solar energy
The quality of battery, FF [%] is most important yardstick, and fill factor, curve factor (Fill Factor, FF) is by comparing
Peak power calculates with the theoretical power (horse-power) exported by open-circuit voltage and short circuit current, and Eta [%] represents efficiency,
It is the most important factor showing solar cell properties, is defined as exporting energy and injecting from the sun
The ratio of energy.
[table 1]
From the result of upper table 1, use the substrate manufacture of the surface treatment method implementing the present invention too
Sun energy battery, compares the substrate carrying out surface process only with Wet-type etching, and its electric property is carried
High.
Claims (7)
1. a surface treatment method for substrate used for solar batteries, comprises the following steps:
First Wet-type etching is carried out for substrate used for solar batteries；
Carry out reactive ion etching；And
Carry out the second Wet-type etching,
Wherein when carrying out described first Wet-type etching, it is 1:2's～4:1～3 that use comprises volume ratio
HF、HNO3And H2The solution of O,
Wherein when carrying out described second Wet-type etching, it is 1:13～17:15～19 that use comprises volume ratio
HF, HNO3And H2The solution of O.
The surface treatment method of substrate used for solar batteries the most according to claim 1, wherein passes through
Described first Wet-type etching, is removed cutting damage simultaneously and the first making herbs into wool processes.
The surface treatment method of substrate used for solar batteries the most according to claim 1, wherein passes through
The etching of described reactive ion carries out the second making herbs into wool process, to form pyramid knot on the surface of described substrate
Structure.
The surface treatment method of substrate used for solar batteries the most according to claim 1, is wherein entering
During row described reactive ion etching, use and comprise Cl2、SF6And O2Gas.
The surface treatment method of substrate used for solar batteries the most according to claim 3, wherein said
The depth-width ratio of pyramid structure is 0.75～1.1.
The surface treatment method of substrate used for solar batteries the most according to claim 1, wherein said
Second Wet-type etching, is carried out 10～60 seconds under conditions of temperature is 20～30 DEG C.
The surface treatment method of substrate used for solar batteries the most according to claim 1, wherein said
Substrate used for solar batteries be the substrate mixed selected from monocrystal substrate, single-crystal region and polycrystalline and
A kind monocrystal substrate in polycrystalline substrate.
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| KR10-2012-0137310 | 2012-11-29 | ||
| KR1020120137310A KR101431730B1 (en) | 2012-11-29 | 2012-11-29 | Texturing method of solar cell wafer |
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| CN113257931B (en) * | 2021-05-12 | 2023-02-10 | 苏州大学 | Preparation method of full-angle light trapping crystalline silicon solar cell suede |
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| CN101478013A (en) * | 2008-12-30 | 2009-07-08 | 无锡尚德太阳能电力有限公司 | Method for producing solar cell silicon wafer suede by reactive ion etching and solar cell produced thereby |
| CN101800264A (en) * | 2010-02-20 | 2010-08-11 | 山东力诺太阳能电力股份有限公司 | Process for texturing crystalline silicon solar cell by dry etching |
| CN102185035A (en) * | 2011-05-04 | 2011-09-14 | 山东力诺太阳能电力股份有限公司 | Process for preparing crystalline silicon solar cell by secondary texturing method |
| CN102468371A (en) * | 2011-12-15 | 2012-05-23 | 江苏腾晖电力科技有限公司 | Texturing method of quasi-single crystal silicon wafer |
| CN102623546A (en) * | 2011-01-30 | 2012-08-01 | 无锡尚德太阳能电力有限公司 | Silicon chip texturing method and solar cell manufactured through using the method |
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| JP2005150614A (en) * | 2003-11-19 | 2005-06-09 | Sharp Corp | Solar battery, and manufacturing method thereof |
| DE102011050136A1 (en) * | 2010-09-03 | 2012-03-08 | Schott Solar Ag | Process for the wet-chemical etching of a silicon layer |
| KR20120037121A (en) * | 2010-10-11 | 2012-04-19 | 엘지전자 주식회사 | Method for manufacturing solar cell |
| KR20120090449A (en) * | 2011-02-08 | 2012-08-17 | 삼성전자주식회사 | Solar cell and method of manufacturing the same |
| KR101779057B1 (en) * | 2011-03-18 | 2017-09-18 | 주성엔지니어링(주) | Wafer type solar cell and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101478013A (en) * | 2008-12-30 | 2009-07-08 | 无锡尚德太阳能电力有限公司 | Method for producing solar cell silicon wafer suede by reactive ion etching and solar cell produced thereby |
| CN101800264A (en) * | 2010-02-20 | 2010-08-11 | 山东力诺太阳能电力股份有限公司 | Process for texturing crystalline silicon solar cell by dry etching |
| CN102623546A (en) * | 2011-01-30 | 2012-08-01 | 无锡尚德太阳能电力有限公司 | Silicon chip texturing method and solar cell manufactured through using the method |
| CN102185035A (en) * | 2011-05-04 | 2011-09-14 | 山东力诺太阳能电力股份有限公司 | Process for preparing crystalline silicon solar cell by secondary texturing method |
| CN102468371A (en) * | 2011-12-15 | 2012-05-23 | 江苏腾晖电力科技有限公司 | Texturing method of quasi-single crystal silicon wafer |
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| KR20140075026A (en) | 2014-06-19 |
| CN103849937A (en) | 2014-06-11 |
| JP2014107551A (en) | 2014-06-09 |
| JP5745598B2 (en) | 2015-07-08 |
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