CN107895744A - A kind of polysilicon chip for solar cell and preparation method thereof - Google Patents

A kind of polysilicon chip for solar cell and preparation method thereof Download PDF

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Publication number
CN107895744A
CN107895744A CN201711107387.0A CN201711107387A CN107895744A CN 107895744 A CN107895744 A CN 107895744A CN 201711107387 A CN201711107387 A CN 201711107387A CN 107895744 A CN107895744 A CN 107895744A
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China
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polysilicon chip
inverted pyramid
pyramid structure
copper
polysilicon
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Inventor
吴俊桃
刘尧平
陈伟
陈全胜
赵燕
王燕
杜小龙
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Institute of Physics of CAS
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Institute of Physics of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • H01L31/02363Special surface textures of the semiconductor body itself, e.g. textured active layers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy

Abstract

The invention provides polysilicon chip for solar cell and preparation method thereof, belongs to solar cell preparing technical field.Polysilicon chip has making herbs into wool surface, the making herbs into wool surface is by a series of independent, close arrangements, the suede structure that there is the class inverted pyramid structure of micron-scale to form, wherein, it is different for the different crystal grain of polysilicon chip, the opening direction of the class inverted pyramid structure.A kind of polysilicon chip for solar cell provided by the invention, crystalline substance are spent substantially, have the making herbs into wool surface being made up of a series of class inverted pyramid structure of micron-scales, and its reflectivity is less than 20%.The preparation method of polysilicon chip provided by the invention, technique is simple, suitable for inexpensive large-scale production.

Description

A kind of polysilicon chip for solar cell and preparation method thereof
Technical field
The present invention relates to solar cell preparing technical field, more particularly to a kind of polysilicon for solar cell Piece and preparation method thereof.
Background technology
Solar energy power generating is that the energy of favor is enjoyed in clean reproducible energy, and crystal silicon solar battery is using too It is positive can one of effective means, crystal silicon battery global photovoltaic market all the time in occupation of more than 80% share, wherein, polycrystalline connects The continuous main flow for turning into crystal silicon product for many years.With the development of photovoltaic industry, it is always big to reduce production cost, raising conversion efficiency Family's concern, in recent years, due to the appearance of Buddha's warrior attendant line cutting technology so that silicon chip monolithic cost reduces 0.4-0.6 members, by Gradually turn into the microtomy of main flow.But popularization of the diamond wire microtomy in terms of polycrystalline is encountered and greatly hindered, this is Because the presence of surface non-crystalline silicon blocks HF/HNO3Effective making herbs into wool of system, and Buddha's warrior attendant line cutting technology has been in terms of monocrystalline Popularized in an all-round way through realizing.
Polysilicon chip, generally use HF/HNO are cut for traditional mortar3Mixed solution is existed by isotropic etching Silicon chip surface formed micron-scale pit structure come to silicon chip surface carry out texture, but its to light be reflected in 20% with On.With the deep development of photovoltaic industry, a kind of new cutting technique-Buddha's warrior attendant line cutting technology, because its production cost is low, cuts Cut that speed is fast, Successful utilization in monocrystalline silicon piece, gradually substitutes mortar cutting technique simultaneously to the various advantages such as small to silicon chip damage As main flow cutting technique.However, regrettably Buddha's warrior attendant line cutting technology can not be applied well and polysilicon chip, reason exist One layer of amorphous silicon layer be present in its surface of Buddha's warrior attendant wire cutting polysilicon chip, hinder wet etching and polysilicon chip surface is knitted Structure, it is set to be reflected in more than 30% to light.
Inverted pyramid structure has excellent reflection preventing ability, and about 40% incident light will carry out triple reflection, can So that reflectivity is reduced into 5%, and its structure size is suitable with positive pyramid size, will not cause compound increase, in view of Excellent sunken light ability and good architectural characteristic so that inverted pyramid structure is widely used in efficient crystal silicon solar electricity In the research in pond.But up to the present also without can be with the inverted pyramid process for etching of industrialization, existing process for etching be all It is more complicated, it is necessary to use the technologies such as photoetching, mask, laser, be unsuitable for inexpensive large-scale production.
In view of the problem present on, in order to reduce cost, increases utilization of the Buddha's warrior attendant wire cutting polysilicon chip to sunshine, The conversion efficiency of Buddha's warrior attendant wire cutting polycrystal silicon cell is improved, promotes the development of Buddha's warrior attendant line cutting technology, needs a kind of new be used for badly The Buddha's warrior attendant wire cutting polysilicon chip of solar cell.
The content of the invention
It is an object of the present invention to provide a kind of polysilicon chip for solar cell, the polysilicon platelet is spent bright It is aobvious, there is the making herbs into wool surface being made up of a series of class inverted pyramid structure of micron-scales, its reflectivity is less than 20%.
Another object of the present invention is to provide for a kind of preparation method of the polysilicon chip for solar cell, its work Skill is simple, suitable for inexpensive large-scale production.
Especially, the invention provides a kind of polysilicon chip for solar cell, there is making herbs into wool surface, the making herbs into wool Surface is a series of suede structure being made up of independent, close arrangements, the class inverted pyramid structure with micron-scale, wherein, For the different crystal grain of polysilicon chip, the opening direction of the class inverted pyramid structure is different.
Alternatively, the making herbs into wool surface of the polysilicon chip is made by being etched in acid Woolen-making liquid, the acid Woolen-making liquid In contain oxidant, the excessive copper nano particles that the oxidant is used to be formed on silicon face are oxidized to form Cu2+And then Avoid being formed the progress of fine and close copper film obstruction etching in silicon chip surface.
Alternatively, the orientation of the corresponding crystal grain of the opening direction of the class inverted pyramid structure is consistent.
Alternatively, the opening shape of the class inverted pyramid structure includes triangle, quadrangle or hexagon;The polycrystalline Silicon chip has the first crystal orientation, the second crystal orientation, the 3rd crystal orientation and the 4th crystal orientation;
For the crystal grain of the second crystal orientation of the polysilicon chip, the opening of the class inverted pyramid structure is triangle;It is right The crystal grain of the 3rd crystal orientation, the 4th crystal orientation in the polysilicon chip, the opening of the class inverted pyramid structure is quadrangle;For The crystal grain of first crystal orientation of the polysilicon chip, the opening of the class inverted pyramid structure is hexagon.
Alternatively, the average reflectance on the making herbs into wool surface is less than 20%;
Alternatively, the average reflectance on the making herbs into wool surface is 5%-20%.
Alternatively, a length of 1~10 μm of the opening edge of the class inverted pyramid structure, constructional depth are 1~10 μm.
Present invention also offers a kind of preparation method of the polysilicon chip for solar cell, by by the silicon after cleaning Piece is dipped to etch in acid Woolen-making liquid and obtained;Wherein, the acid Woolen-making liquid includes copper ion source, fluoride sources and can Copper is oxidized to the oxidant of copper ion.
Alternatively, the copper ion source is used to provide the copper ion that concentration is 0.1~30.0mmol/L, and fluoride sources are used for The fluorine ion that concentration is 0.4~11.0mol/L is provided, the concentration of oxidant is 0.1~5.0mol/L.
Alternatively, the copper ion source is the one or more in copper chloride, copper sulphate and copper nitrate;The oxidant is One or more in potassium permanganate, KBr, persulfate and hydrogen peroxide.
Alternatively, temperature during the acid Woolen-making liquid etching is 30 DEG C~80 DEG C, and etch period is 3 minutes~20 points Clock.
A kind of polysilicon chip for solar cell provided by the invention and preparation method thereof, can be in lower temperature Under, acid Woolen-making liquid is used in the short period, it is different that independent, close arrangement, opening direction are formed on polysilicon difference crystal grain Class inverted pyramid structure, cause each crystal grain reflectivity bigger difference occur.The class inverted pyramid structure of the polysilicon chip has Micron-scale, the reflectivity of incident light can be reduced to 20%, while be greatly enhanced the efficiency of battery.
Polysilicon chip provided by the invention and preparation method thereof, solve the problems, such as the making herbs into wool of diamond wire polysilicon surface, can Promote the development of Buddha's warrior attendant line cutting technology.Meanwhile the polysilicon chip after the making herbs into wool can be used after cell piece and component is prepared into In facade decoration and distributed photovoltaic battery.
According to the accompanying drawings will be brighter to the detailed description of the specific embodiment of the invention, those skilled in the art Above-mentioned and other purposes, the advantages and features of the present invention.
Brief description of the drawings
Some specific embodiments of the present invention are described in detail by way of example, and not by way of limitation with reference to the accompanying drawings hereinafter. Identical reference denotes same or similar part or part in accompanying drawing.It should be appreciated by those skilled in the art that these What accompanying drawing was not necessarily drawn to scale.In accompanying drawing:
The class inverted pyramid that Fig. 1 obtains for the polysilicon chip according to one embodiment of the invention after etched on making herbs into wool surface SEM (scanning electron microscope, SEM) figure of structure;
Fig. 2 is that the class inverted pyramid structure on the different crystal grain in the making herbs into wool surface shown in Fig. 1 corresponds to different opening shapes Shape figure;
Fig. 3 is the reflectivity comparison diagram of the different crystal grain in the making herbs into wool surface shown in Fig. 1;
Fig. 4 is the variation diagram of reflectivity of the polysilicon chip after making herbs into wool and deposited silicon nitride antireflective coating shown in Fig. 1;
Fig. 5 be one embodiment of the invention making herbs into wool after polysilicon chip outside drawing;
The outside drawing for the cell piece that Fig. 6 is prepared into for polysilicon chip after the making herbs into wool of one embodiment of the invention;
Fig. 7 is variation diagram of the polysilicon chip of the embodiment of the present invention 2, embodiment 3 and embodiment 4 through making herbs into wool back reflection rate.
Embodiment
In order to solve the problems, such as the Buddha's warrior attendant wire cutting polycrystalline silicon texturing complex process of prior art and reflectivity is high, this hair It is bright to propose a kind of acid Woolen-making liquid for ablation of solar cells silicon chip.In one embodiment of the invention, the acidity Woolen-making liquid includes copper ion source, fluoride sources and the oxidant that copper can be oxidized to copper ion.Wherein copper ion source is used for There is provided concentration be 0.1~30.0mmol/L copper ion, fluoride sources be used for provide concentration be 0.4~11.0mol/L fluorine from Son, the concentration of oxidant is 0.1~5.0mol/L oxidants.
The class inverted pyramid that Fig. 1 obtains for the polysilicon chip according to one embodiment of the invention after etched on making herbs into wool surface SEM (scanning electron microscope, SEM) figure of structure.Fig. 2 is the making herbs into wool table shown in Fig. 1 The class inverted pyramid structure on different crystal grain in face corresponds to different opening shape figures.As depicted in figs. 1 and 2, the present invention carries A kind of polysilicon chip for solar cell supplied, has making herbs into wool surface.The making herbs into wool surface of polysilicon chip is by a series of only Vertical, close arrangement, the suede structure that there is the class inverted pyramid structure of micron-scale to form.Wherein, for polysilicon chip not Same crystal grain, in other words, for the crystal grain of the different crystal orientations of polysilicon chip, the opening direction of class inverted pyramid structure is different.Polycrystalline The making herbs into wool surface of silicon chip is made by acid Woolen-making liquid etching.Contain oxidant in acid Woolen-making liquid.Oxidant is used to cause silicon The excessive copper nano particles formed on surface are oxidized to form Cu2+, and then avoid forming fine and close copper film resistance on polysilicon chip surface Hinder the progress of etching.
Specifically, as shown in Fig. 2 the orientation of the corresponding crystal grain of the opening direction of class inverted pyramid structure is consistent.Class The opening shape of inverted pyramid structure includes triangle, quadrangle, hexagon etc..The polysilicon chip has the first crystal orientation, the Two crystal orientation, the 3rd crystal orientation and the 4th crystal orientation.For example, the first crystal orientation of polysilicon chip is<110>Crystal orientation, the second of polysilicon chip are brilliant Xiang Wei<111>Crystal orientation, the 3rd crystal orientation of polysilicon chip are<112>Crystal orientation, the 4th crystal orientation of polysilicon chip are<113>Crystal orientation.It is right In the crystal grain of the second crystal orientation of polysilicon chip, the opening of class inverted pyramid structure is triangle;It is brilliant for the 3rd of polysilicon chip the To the crystal grain of, the 4th crystal orientation, the opening of class inverted pyramid structure is quadrangle;For the crystal grain of the first crystal orientation of polysilicon chip, The opening of class inverted pyramid structure is hexagon.
A length of 1~10 μm of the opening edge of class inverted pyramid structure, constructional depth are 1~10 μm.Fig. 3 is the system shown in Fig. 1 The reflectivity comparison diagram of different crystal grain in suede surface.Fig. 4 is the polysilicon chip shown in Fig. 1 through making herbs into wool and deposited silicon nitride anti-reflection The variation diagram for the reflectivity penetrated after film.As shown in Figure 3 and Figure 4, the class inverted pyramid structure of micron-scale, can be by the anti-of incident light The rate of penetrating is reduced within 20%, while is greatly enhanced the efficiency of battery.
The preparation method of a kind of polysilicon chip for solar cell provided by the invention, by the way that silicon chip is dipped into acid In property Woolen-making liquid, and regulate and control the pattern of etching and depth by controlling the concentration of copper ion source, fluoride sources and oxidant Degree, so as to form in lower temperature and on silicon chip surface the class inverted pyramid structure of fine and close arrangement, effectively solution in the short period Diamond wire of having determined cuts the making herbs into wool problem of polysilicon, can promote the development of diamond wire microtomy.
Reason is in acid Woolen-making liquid, containing Cu2+Copper ion source mainly play catalyst, Cu2+In the solution Because potential is relatively low, electronics can be obtained from the valence band of silicon it is reduced into copper particle and be deposited on silicon chip surface, and silicon loses electronics It is oxidized to silica, fluoride sources and silicon dioxde reaction in solution, generates water-soluble product, and then realizes pair Effective etching of silicon chip.Temperature is higher during due to etching so that Cu2+The speed of electronics is obtained, is so easy in silicon chip table The copper film of densification is formed on face, hinders etching of the fluorine ion to silicon chip.The present inventor in acid Woolen-making liquid by drawing Enter oxidant so that the excessive copper nano particles formed on silicon face are oxidized to form Cu2+, and then avoid in silicon chip surface Form the progress that fine and close copper film hinders etching.The present invention has efficiently controlled metal copper nano granules by the use of oxidant Separate out and dissolve, and then efficiently controlled etching effect, shorten etch period.
It is of the invention by the copper ion in acid Woolen-making liquid in order to carry out effective making herbs into wool to Buddha's warrior attendant wire cutting polysilicon surface Concentration control be 0.1~30.0mmol/L, and it is 0.4~11.0mol/L that the concentration of fluorine ion, which controls, while by the concentration of oxidant Control as 0.1~5.0mol/L.Wherein, copper ion can obtain electronics from silicon face, silica is melted into silica, while certainly Body is reduced into copper nano particles, and then realizes the catalysis etching to silicon chip.Copper ion concentration is too high or too low, can all influence pair Diamond wire cuts effective etching of polysilicon chip.
Main function of the fluorine ion in acid Woolen-making liquid is that the silica formed with reaction is reacted and then generated The product of water is dissolved in, promotes the progress entirely etched.If the fluorinion concentration in acid Woolen-making liquid is too low, copper ion catalysis shape Into silica can not be efficiently removed, and then prevent, to the further etching of silicon, thus can not effectively to make silicon chip Suede, preferable class inverted pyramid structure can not be obtained.If the fluorinion concentration in acid Woolen-making liquid is too high, etching speed can be caused Spend soon, nano-pore structure can be formed in silicon chip surface, and then cannot get class inverted pyramid structure.
The excessive copper nano particles of precipitation are mainly oxidized to copper ion and silica are turned into dioxy by the effect of oxidant SiClx.If oxidant concentration is too low, it is excessive to occur that copper nanoparticle separates out, causes the appearance of fine and close copper film, hinders to carve The progress of erosion.If oxidant concentration is too high, reaction is than very fast, it may appear that the problem of silicon face copper nano particles can not separate out, Cause etching efficiency too low, class inverted pyramid structure can not be obtained.
It was found by the inventors of the present invention that the structure that metal catalytic etching preparation method obtains typically is being used as nano junction Structure, this easily forms a large amount of dead layer structures when solar cell is prepared and is difficult to be passivated, and causes its surface recombination and Russia Have a rest compound increase, influence the lifting of solar cell electrical property.And the metal catalytic lithographic method used in the present invention, due to Creatively the concentration that reagent is etched in acid Woolen-making liquid is selected and controlled within the above range, and then acquisition has micron meter The making herbs into wool surface of very little class inverted pyramid structure.And the class inverted pyramid structure of the micron-scale of fine and close arrangement can avoid largely The appearance of dead layer, surface recombination and auger recombination are reduced, while existing solar cell preparation technology can be matched, reduced The reflectivity of making herbs into wool surface incident light, the conversion efficiency of battery is substantially increased, promoted Buddha's warrior attendant line cutting technology in polysilicon The development in field.
In order to obtain more preferable suede structure so that the even closer arrangement of class inverted pyramid structure on making herbs into wool surface, volume Size is more homogeneous, and then preferably reduces the reflectivity of silicon chip, it is further preferred that in acid Woolen-making liquid, copper ion Concentration is 4.0mmol/L~20.0mmol/L, and the concentration of fluorine ion is 3.0mol/L~8.0mol/L, and the concentration of oxidant is 0.2mol/L~3.0mol/L.
In the specific embodiment of the present invention, copper ion source is in copper chloride, copper sulphate and copper nitrate It is one or more.One or more of the oxidant in potassium permanganate, KBr, persulfate and hydrogen peroxide.Exemplarily, It will be apparent to those skilled in the art that persulfate can include but is not limited to ammonium persulfate, potassium peroxydisulfate and persulfuric acid Sodium.Of the invention preferably above-mentioned copper ion source and oxidant, but be not limited thereto, if can be ionized in copper ion source come from by Mobile copper ion, oxidant have stronger oxidation, copper nano particles can be oxidized into copper ion.
In another specific embodiment of the present invention, copper ion source is copper nitrate, and fluoride sources are hydrofluoric acid, using double Oxygen water is oxidant, i.e., acid Woolen-making liquid is made up of copper nitrate, hydrofluoric acid and hydrogen peroxide.In a kind of preferred embodiment of the present invention In, the concentration of copper nitrate is 8.0mmol/L, and the concentration of hydrofluoric acid is 4.3mol/L, and the concentration of hydrogen peroxide is 0.5mol/L.Using The acid Woolen-making liquid of the preferred embodiment can obtain the more homogeneous class of volume size to Buddha's warrior attendant wire cutting polycrystalline silicon texturing Inverted pyramid structure, and surface smoother, the whole volume of class inverted pyramid is than more complete.
According to another aspect of the present invention, additionally provide one kind and be used for Buddha's warrior attendant wire cutting polysilicon chip class inverted pyramid making herbs into wool Acid etching method, comprise the following steps:Any of the above-described kind of acid Woolen-making liquid is prepared first, acid Woolen-making liquid is mixed equal It is even, it is not limited to stir, the methods of bubbling;Then, it will treat that making herbs into wool silicon chip is positioned in acid Woolen-making liquid, in certain state of temperature Under, and predetermined etch period, obtain the silicon chip after surface wool manufacturing.
The signified Buddha's warrior attendant wire cutting polysilicon chip for solar cell, both may adapt to N-type monocrystalline in the present invention Silicon, it is also suitable for p type single crystal silicon.Will be after making herbs into wool silicon chip be placed in acid Woolen-making liquid, in fluorine ion, strong oxidizer and Cu nanometers , can be relatively low because Cu nano particles are different with the etch rate in (111) face to Si (100) under the collective effect of particle Temperature and anisotropic etching is formed on a silicon surface in the shorter time, obtained on a silicon surface so as to simply and rapidly only Class inverted pyramid structure vertical, complete, fine and close and with micron-scale, its opening direction are different with crystal grain orientation.
In order to obtain the class inverted pyramid suede structure of the present invention, in the exemplary embodiments of the present invention, acid Woolen-making liquid Temperature be 30 DEG C~80 DEG C scopes, etch period is 3 minutes~20 minutes.If the predetermined temperature of etching is higher than 80 DEG C, meeting It is too fast to there is copper ion precipitation, leads to not the making herbs into wool surface of acquisition class inverted pyramid structure.If the predetermined temperature of etching is low In 30 DEG C, etch rate can be caused excessively slow, nanostructured easily occur, the class for the micron-scale that equally cannot closely arrange is fallen Pyramid structure making herbs into wool surface.If etch period is higher than 20 minutes, the complete class prepared can be fallen because of overetch golden Word tower structure damages, can be too short complete, independent so as to be formed because of etch period if etch period is less than 3 minutes Class inverted pyramid structure.
It is further preferred that predetermined temperature is 40 DEG C~55 DEG C, the scheduled time is 5 minutes~10 minutes.It is specific at one Embodiment in, the predetermined temperature of etching is 45 DEG C, and the scheduled time is 7 minutes.
The inevitably residual fraction organic impurities on silicon chip during due to cutting silicon chip, therefore, will wait to make Suede silicon chip is placed in acid Woolen-making liquid perform etching before, in addition to silicon chip carry out prerinse and washing the step of.Specific bag Include:First silicon chip is sequentially placed into acetone and ethanol and is cleaned by ultrasonic, is placed in the mixed liquor of sulfuric acid solution and hydrogen peroxide solution afterwards Middle heating is boiled, and general heating is kept for 0.5~1 hour after boiling, then is placed in water ultrasonic cleaning.Wherein, sulfuric acid solution is dense Spend for 70wt%, the concentration of hydrogen peroxide solution is 30wt%.The volume ratio of sulfuric acid solution and hydrogen peroxide solution is 3:1.Using third Ketone and EtOH Sonicate cleaning purpose are away to remain in the organic impurities on silicon chip, using sulfuric acid solution and hydrogen peroxide solution
Mixed liquor is cleaned, and the purpose is to remove the metal impurities on silicon chip surface.Finally using deionized water ultrasound Cleaning purpose is to remove the decoction that prerinse is remained on silicon chip surface.By prerinse and washing, lifting cell photoelectric is turned It is significant to change efficiency.
Fig. 5 be one embodiment of the invention making herbs into wool after polysilicon chip outside drawing.Fig. 6 is one embodiment of the invention The outside drawing for the cell piece that polysilicon chip is prepared into after making herbs into wool.It is that the sun is used for according to one kind provided by the invention as shown in Figure 5 The polysilicon chip of energy battery.It is illustrated in figure 6 and is prepared into solar battery sheet.Obtained using the etching method of the present invention Solar battery sheet obtains solar battery sheet relative to the etching method of routine, has short circuit current height and solar cell The advantages of high conversion efficiency.
Factor in view of matching existing solar cell preparation technology, acid etching method provided by the present invention also wrap Include and the silicon chip after making herbs into wool is put into the step of being cleaned by ultrasonic in nitric acid or chloroazotic acid to remove making herbs into wool surface metal covering.To removing Silicon chip after metal covering is cleaned by ultrasonic with deionized water, is dried up afterwards using high pure nitrogen.
Technical scheme is further illustrated with reference to more specifically embodiment:
Embodiment 1
1) surface cleaning step
P-type silicon piece that size is 156mm × 156mm (resistivity is the Ω cm of 1 Ω cm~3) is taken, is first sequentially placed into third It is cleaned by ultrasonic 5 minutes in ketone, is put into ethanol and is cleaned by ultrasonic 5 minutes, is placed in the mixing of sulfuric acid solution and hydrogen peroxide solution afterwards (concentration of sulfuric acid solution is 70wt%, and the concentration of hydrogen peroxide solution is 30wt%, sulfuric acid solution and hydrogen peroxide solution body in liquid Product is than being 3:1), silicon chip heating is boiled and kept for 0.5 hour, is finally cleaned by ultrasonic with deionized water clean.
2) etch step
The clean silicon chip of prerinse in step 1) and washing is immersed to the acidity being made up of copper nitrate, hydrofluoric acid and hydrogen peroxide (wherein, the concentration of copper nitrate is 8.0mmol/L, and the concentration of hydrofluoric acid is 4.3mol/L, and the concentration of hydrogen peroxide is in Woolen-making liquid 0.5mol/L), reaction temperature is 45 DEG C, is etched 7 minutes.
03) post-processing stages
By the silicon chip extracting after making herbs into wool in step 2), the nitric acid for being 69wt% with concentration is cleaned by ultrasonic to remove surface covering Metal, be then cleaned by ultrasonic again with deionized water, dried up with high pure nitrogen, you can obtain with class inverted pyramid structure gold Firm wire cutting multicrystalline silicon substrate.Its SEM (SEM) figure with class inverted pyramid surface texture obtained, ginseng See Fig. 1.As can be seen that independent, complete, the close row of the class inverted pyramid structure obtained using the acid etching method of the present invention Cloth, and its opening direction is different and different with crystal grain, sees Fig. 2-Fig. 6.
Embodiment 2
1) surface cleaning step
P-type silicon piece that size is 156mm × 156mm (resistivity is the Ω cm of 1 Ω cm~3) is taken, is first sequentially placed into third It is cleaned by ultrasonic 5 minutes in ketone, is put into ethanol and is cleaned by ultrasonic 5 minutes, is placed in the mixing of sulfuric acid solution and hydrogen peroxide solution afterwards (concentration of sulfuric acid solution is 70wt%, and the concentration of hydrogen peroxide solution is 35wt%, sulfuric acid solution and hydrogen peroxide solution body in liquid Product is than being 3:1), silicon chip heating is boiled and kept for 0.5 hour, is finally cleaned by ultrasonic with deionized water clean.
2) etch step
The clean silicon chip of prerinse in step 1) and washing is immersed to the acidity being made up of copper nitrate, hydrofluoric acid and hydrogen peroxide (wherein, the concentration of copper nitrate is 4.0mmol/L, and the concentration of hydrofluoric acid is 6.0mol/L, and the concentration of hydrogen peroxide is in Woolen-making liquid 0.5mol/L), reaction temperature is 50 DEG C, is etched 15 minutes.
3) post-processing stages
By the silicon chip extracting after making herbs into wool in step 2), the nitric acid for being 69wt% with concentration is cleaned by ultrasonic to remove surface covering Metal, be then cleaned by ultrasonic again with deionized water, dried up with high pure nitrogen, you can obtain with class inverted pyramid structure gold Firm wire cutting multicrystalline silicon substrate.
Comparative example 1, its nitric acid copper concentration and hydrofluoric acid concentration and etch period, reaction temperature etc. are become Change.In example 2, the concentration of copper nitrate is reduced to 4.0mmol/L so that the speed of etching slows down, and the reaction time should fit Work as lengthening.
Embodiment 3
1) surface cleaning step
P-type silicon piece that size is 156mm × 156mm (resistivity is the Ω cm of 1 Ω cm~3) is taken, is first sequentially placed into third It is cleaned by ultrasonic 5 minutes in ketone, is put into ethanol and is cleaned by ultrasonic 5 minutes, is placed in the mixing of sulfuric acid solution and hydrogen peroxide solution afterwards (concentration of sulfuric acid solution is 70wt%, and the concentration of hydrogen peroxide solution is 35wt%, sulfuric acid solution and hydrogen peroxide solution body in liquid Product is than being 3:1), silicon chip heating is boiled and kept for 0.5 hour, is finally cleaned by ultrasonic with deionized water clean.
2) etch step
The clean silicon chip of prerinse in step 1) and washing is immersed to the acidity being made up of copper nitrate, hydrofluoric acid and hydrogen peroxide (wherein, the concentration of copper nitrate is 20mmol/L, and the concentration of hydrofluoric acid is 7.0mol/L, and the concentration of hydrogen peroxide is in Woolen-making liquid 2.0mol/L), reaction temperature is 40 DEG C, is etched 5 minutes.
3) post-processing stages
By the silicon chip extracting after making herbs into wool in step 2), the nitric acid for being 69wt.% with concentration is cleaned by ultrasonic to be covered with removing surface The metal of lid, is then cleaned by ultrasonic with deionized water again, is dried up with high pure nitrogen, you can is obtained with class inverted pyramid structure Buddha's warrior attendant wire cutting multicrystalline silicon substrate.
Comparative example 1, its nitric acid copper concentration and hydrofluoric acid concentration, reaction temperature and etch period are changed. In embodiment 3, the concentration of copper nitrate is increased to 20.0mmol/L so that the speed of etching is accelerated, and the reaction time should be appropriate Shorten, you can obtain the Buddha's warrior attendant wire cutting multicrystalline silicon substrate with class inverted pyramid structure.
Embodiment 4
1) surface cleaning step
P-type silicon piece that size is 156mm × 156mm (resistivity is the Ω cm of 1 Ω cm~3) is taken, is first sequentially placed into third It is cleaned by ultrasonic 5 minutes in ketone, is put into ethanol and is cleaned by ultrasonic 5 minutes, is placed in the mixing of sulfuric acid solution and hydrogen peroxide solution afterwards (concentration of sulfuric acid solution is 70wt%, and the concentration of hydrogen peroxide solution is 35wt%, sulfuric acid solution and hydrogen peroxide solution body in liquid Product is than being 3:1), silicon chip heating is boiled and kept for 0.5 hour, is finally cleaned by ultrasonic with deionized water clean.
2) etch step
The clean silicon chip of prerinse in step 1) and washing is immersed to the acidity being made up of copper nitrate, hydrofluoric acid and hydrogen peroxide (wherein, the concentration of copper nitrate is 25mmol/L, and the concentration of hydrofluoric acid is 5.0mol/L, and the concentration of hydrogen peroxide is in Woolen-making liquid 3.0mol/L), reaction temperature is 55 DEG C, is etched 3 minutes.
3) post-processing stages
By the silicon chip extracting after making herbs into wool in step 2), the nitric acid for being 69wt% with concentration is cleaned by ultrasonic to remove surface covering Metal, be then cleaned by ultrasonic again with deionized water, dried up with high pure nitrogen, you can obtain with class inverted pyramid structure gold Firm wire cutting multicrystalline silicon substrate.
Comparative example 1, each constituent concentration of its Woolen-making liquid, reaction temperature and etch period are changed.Implementing In example 4, the concentration of copper nitrate is increased to 25.0mmol/L, and also there occurs very big change for the concentration of corresponding hydrogen peroxide so that The speed of etching is accelerated, and the reaction time shortens, you can obtains the Buddha's warrior attendant wire cutting multicrystalline silicon substrate with class inverted pyramid structure.
In contrast to embodiment 1, embodiment 2, embodiment 3, the nitric acid copper concentration of embodiment 4 it is different and using various concentrations Oxidant, while etch period is also different.The nitric acid copper concentration increase of embodiment 4 so that reaction ratio is very fast, therefore more Can forms suede structure in short time.
The present invention is totally reflected integrating sphere using Varian Cary 5000 and the surface reflectivity of above-mentioned sample is tested, Its average reflectance is shown in Fig. 7 between 18%-25%.
Monocrystalline silicon piece after embodiment 1-4 making herbs into wool is prepared into solar battery sheet using conventional method, including entered successively Row diffusion, remove phosphorosilicate glass, etching trimming, coated with antireflection film, prepare electrode, characteristic test.Silicon chip after wherein spreading Sheet resistance is 80 Ω/sq, and the silicon nitride anti-reflecting film of deposition is 80nm.Using halm testers measure solar battery sheet Uoc, Jsc, FF, Eff, specific performance are shown in Table 1.
Table 1
For embodiment 1, the reflectivity after reflectivity and depositing antireflection film after its making herbs into wool is obtained for greatly Reduce, refer to Fig. 4.
From table 1 it follows that technical scheme is used in embodiment 1-4, by controlling in acid Woolen-making liquid Copper ion salting liquid, the concentration in fluoride ion source and hydrogen peroxide, etching temperature and time, preferably control etching pattern and Depth, therefore under room temperature state and making herbs into wool surface can be performed etching in the short period, it is independent, complete and tight so as to obtain The class inverted pyramid structure matte of solid matter cloth, compared with the vermicular texture that conventional polycrystalline acid making herbs into wool is prepared, greatly drop Low reflectivity, improves the conversion efficiency of battery, efficiently solves the making herbs into wool problem that diamond wire cuts polysilicon, promoted Buddha's warrior attendant The development of line microtomy.
Therefore, acid Woolen-making liquid and etching method technique of the invention is simple, and cost is cheap, easy to operate, application conditions Extensively, a step is only needed just to obtain class inverted pyramid structure in very short time on silicon chip under lower temperature conditions, solve Diamond wire cuts the making herbs into wool problem of polysilicon.
A kind of polysilicon chip for solar cell provided by the invention and preparation method thereof, can be in lower temperature Under, acid Woolen-making liquid is used in the short period, it is different that independent, close arrangement, opening direction are formed on polysilicon difference crystal grain Class inverted pyramid structure, cause each crystal grain reflectivity bigger difference occur.The class inverted pyramid structure of the polysilicon chip has Micron-scale, the reflectivity of incident light can be reduced to 20%, while be greatly enhanced the efficiency of battery.
Polysilicon chip provided by the invention and preparation method thereof, solve the problems, such as the making herbs into wool of diamond wire polysilicon surface, can Promote the development of Buddha's warrior attendant line cutting technology.Meanwhile the polysilicon chip after the making herbs into wool can be used after cell piece and component is prepared into In facade decoration and distributed photovoltaic battery.
So far, although those skilled in the art will appreciate that detailed herein have shown and described multiple showing for the present invention Example property embodiment, still, still can be direct according to present disclosure without departing from the spirit and scope of the present invention It is determined that or derive many other variations or modifications for meeting the principle of the invention.Therefore, the scope of the present invention is understood that and recognized It is set to and covers other all these variations or modifications.

Claims (10)

1. a kind of polysilicon chip for solar cell, there is making herbs into wool surface, it is characterised in that the making herbs into wool surface is by one Serial independent, close arrangement, the suede structure that there is the class inverted pyramid structure of micron-scale to form, wherein, for polysilicon The different crystal grain of piece, the opening direction of the class inverted pyramid structure are different.
2. polysilicon chip according to claim 1, it is characterised in that the making herbs into wool surface of the polysilicon chip is made by acidity Suede liquid etching is made, and oxidant is contained in the acid Woolen-making liquid, and the oxidant is used to cause the excess formed on silicon face Copper nano particles are oxidized to form Cu2+And then avoid being formed the progress of fine and close copper film obstruction etching in silicon chip surface.
3. polysilicon chip according to claim 1, it is characterised in that the opening direction of the class inverted pyramid structure and its The orientation of corresponding crystal grain is consistent.
4. polysilicon chip according to claim 1, it is characterised in that the opening shape of the class inverted pyramid structure includes Triangle, quadrangle or hexagon;The polysilicon chip has the first crystal orientation, the second crystal orientation, the 3rd crystal orientation and the 4th crystal orientation;
For the crystal grain of the second crystal orientation of the polysilicon chip, the opening of the class inverted pyramid structure is triangle;For institute The 3rd crystal orientation, the crystal grain of the 4th crystal orientation of polysilicon chip are stated, the opening of the class inverted pyramid structure is quadrangle;For described The crystal grain of first crystal orientation of polysilicon chip, the opening of the class inverted pyramid structure is hexagon.
5. polysilicon chip according to claim 1, it is characterised in that the average reflectance on the making herbs into wool surface is less than 20%;
Alternatively, the average reflectance on the making herbs into wool surface is 5%-20%.
6. polysilicon chip according to claim 1, it is characterised in that a length of 1 μ of opening edge of the class inverted pyramid structure M~10 μm, constructional depth are 1 μm~10 μm.
7. the preparation method of a kind of polysilicon chip for solar cell, it is characterised in that by the way that the silicon chip after cleaning is soaked Bubble is etched into acid Woolen-making liquid and obtained;Wherein, the acid Woolen-making liquid includes copper ion source, fluoride sources and can be by copper It is oxidized to the oxidant of copper ion.
8. the preparation method of polysilicon chip according to claim 7, it is characterised in that the copper ion source is dense for providing The copper ion for 0.1~30.0mmol/L is spent, fluoride sources are used to provide the fluorine ion that concentration is 0.4~11.0mol/L, oxidation The concentration of agent is 0.1~5.0mol/L.
9. the preparation method of polysilicon chip according to claim 7, it is characterised in that the copper ion source be copper chloride, One or more in copper sulphate and copper nitrate;The oxidant is in potassium permanganate, KBr, persulfate and hydrogen peroxide It is one or more.
10. the preparation method of polysilicon chip according to claim 7, it is characterised in that during the acid Woolen-making liquid etching Temperature be 30 DEG C~80 DEG C, etch period be 3 minutes~20 minutes.
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