CN106611799B - A kind of two-sided crystal silicon solar energy battery of inkjet printing and preparation method thereof - Google Patents

A kind of two-sided crystal silicon solar energy battery of inkjet printing and preparation method thereof Download PDF

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CN106611799B
CN106611799B CN201710020815.XA CN201710020815A CN106611799B CN 106611799 B CN106611799 B CN 106611799B CN 201710020815 A CN201710020815 A CN 201710020815A CN 106611799 B CN106611799 B CN 106611799B
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layer
back side
product obtained
inkjet printing
amorphous
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CN106611799A (en
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黄石明
孙海平
陈文浩
刘仁中
王海超
张斌
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HEFEI HAREON SOLAR TECHNOLOGY Co Ltd
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HEFEI HAREON SOLAR TECHNOLOGY Co Ltd
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Abstract

The invention discloses a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix, the front of P-type silicon matrix is provided with phosphorus-diffused layer, matte texture, reduced passivation resisting film, positive silver electrode, and the back side is provided with nano oxidized silicon layer, amorphous or polycrystalline P+Layer, transparent conductive film layer, back side silver electrode；It can be efficiently modified light absorption and electric current collection, and reduction is optically and electrically lost.The invention also discloses a kind of preparation method of the two-sided crystal silicon solar energy battery of inkjet printing, and it is by increasing nano oxidized silicon layer, amorphous or polycrystalline P+Layer, transparent conductive film layer, form completely black solar cell using inkjet technology, and so as to be efficiently modified light absorption and electric current collection, reduction is optically and electrically lost.

Description

A kind of two-sided crystal silicon solar energy battery of inkjet printing and preparation method thereof
Technical field
The present invention relates to crystal silicon solar energy battery manufacturing technology field, more particularly to a kind of two-sided crystalline silicon of inkjet printing Solar cell and preparation method thereof.
Background technology
With the raising of solar battery technology, its industrialized production develops progressively towards efficient, inexpensive direction.So And two principal elements for restricting solar battery efficiency are respectively optical loss and electricity loss.
In the prior art, efficiently back of the body passivation solar cell is that back of the body passivation is mutually tied with metallized area local heavy doping technology The representative of conjunction, it is advantageous that：
1) there is excellent back reflector：Due to the presence of cell backside deielectric-coating so that internal back reflection from routine Full Al-BSF 65% increases to 92-95%, and its one side increases the absorption of the long glistening light of waves, and the opposing party faces the future the hair of Thin film cell Exhibition provides technical guarantee；
2) the superior passivating back technology of dielectric film：Due to the good passivation of back side deielectric-coating, dielectric film area The back side recombination rate in domain is reduced to 10-50cm/s.
Above-mentioned efficiently back of the body passivation solar battery structure, though early in last century the nineties by Australian new southern Weir Scholar university proposes, and obtains the crystal silicon solar batteries of world record 25%.But because it uses the design of back point contact, So that cell series resistance increases, electricity loss increases, and is unfavorable for light absorption and electric current collection.
The content of the invention
An object of the present invention is to propose a kind of two-sided crystal silicon solar energy battery of inkjet printing, can be efficiently modified Light absorption and electric current collection, reduction are optically and electrically lost.
The second object of the present invention is the preparation method for proposing a kind of two-sided crystal silicon solar energy battery of inkjet printing, its Completely black solar cell is formed using inkjet technology, so as to be efficiently modified light absorption and electric current collection, reduces optics Lost with electricity.
To use following technical scheme up to this purpose, the present invention：
On the one hand, the present invention provides a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix, the P The front of type silicon substrate is provided with phosphorus-diffused layer, and the front of the phosphorus-diffused layer is provided with matte texture, the matte texture Front is provided with reduced passivation resisting film, and the front of the reduced passivation resisting film is provided with positive silver electrode；The back side of the P-type silicon matrix Nano oxidized silicon layer is provided with, the back side of the nano oxidized silicon layer is provided with amorphous or polycrystalline P+Layer, amorphous or the polycrystalline P+ The back side of layer is provided with transparent conductive film layer, and the back side of the transparent conductive film layer is provided with back side silver electrode.
The two-sided crystal silicon solar energy battery of the inkjet printing, by set at the back side of P-type silicon matrix nano oxidized silicon layer, Amorphous or polycrystalline P+Layer and transparent conductive film layer, wherein, the high quality that nano oxidized silicon layer can provide cell backside is blunt Change, and amorphous or polycrystalline P+Layer can be used for forming tunneling structure, then coordinate transparent conductive film layer, can significantly improve battery Back of the body passivation quality and electric current export performance, reduce back side recombination losses and electric current export loss；Further, coordinate with P-type silicon The positive matte texture of matrix, increase the light absorption and electric current collection of battery, reduction is optically and electrically lost, and improves crystal The conversion efficiency of silicon solar cell.
Preferably, the P-type silicon matrix is p-type silicon chip, and its resistivity is 0.5-6 Ω cm；For example, 0.5 Ω cm, 0.8Ω·cm、1.0Ω·cm、1.3Ω·cm、1.5Ω·cm、1.9Ω·cm、2.0Ω·cm、2.2Ω·cm、2.6Ω· cm、2.8Ω·cm、3.0Ω·cm、3.5Ω·cm、3.7Ω·cm、4.0Ω·cm、4.1Ω·cm、4.4Ω·cm、4.9 Ω cm, 5.0 Ω cm, 5.6 Ω cm or 6.0 Ω cm etc..
Preferably, the reduced passivation resisting film is SiNx passivating films or SiO2/ SiNx overlayer passivation films.
Preferably, the thickness of the nano oxidized silicon layer is 0.3-5nm；For example, 0.3nm, 0.35nm, 0.5nm, 0.8nm、1.0nm、1.1nm、1.3nm、1.6nm、1.9nm、2.0nm、2.2nm、2.4nm、2.7nm、3.0nm、3.3nm、 3.5nm, 3.9nm, 4.0nm, 4.6nm, 4.7nm or 5.0nm etc..
Preferably, the thickness of amorphous or polycrystalline the p+ layers is 10-1000nm, doping concentration 1017~1022cm-3；Example As thickness be 10nm, 13nm, 17nm, 20nm, 25nm, 30nm, 36nm, 40nm, 47nm, 50nm, 51nm, 58nm, 60nm, 76nm、82nm、94nm、100nm、113nm、119nm、125nm、134nm、150nm、176nm、181nm、190nm、200nm、 222nm、235nm、245nm、260nm、279nm、298nm、315nm、340nm、400nm、416nm、482nm、500nm、 538nm、597nm、600nm、636nm、684nm、700nm、756nm、800nm、837nm、900nm、901nm、957nm、 968nm, 978nm or 1000nm etc., such as doping concentration are 1017cm-3、1018cm-3、1019cm-3、1020cm-3、1021cm-3Or 1022cm-3Deng.
Preferably, the thickness of the transparent conductive film layer is 10-500nm；For example, 10nm, 13nm, 15nm, 19nm, 25nm、30nm、34nm、36nm、40nm、49nm、65nm、71nm、75nm、83nm、90nm、100nm、103nm、106nm、 109nm、110nm、126nm、137nm、142nm、168nm、179nm、198nm、200nm、215nm、236nm、249nm、 268nm、300nm、306nm、325nm、378nm、395nm、400nm、411nm、456nm、468nm、479nm、480nm、 485nm, 498nm or 500nm etc..
On the other hand, the present invention also provides a kind of preparation method of the two-sided crystal silicon solar energy battery of inkjet printing, including Following steps：
1) damaging layer and the making herbs into wool of P-type silicon matrix surface are removed；
2) surface of the product obtained in step 1) performs etching, and forms completely black convex-concave surface structure, and carry out matte Modification, form matte texture；
3) surface of the product obtained in step 2) carries out phosphorus diffusion knot, forms phosphorus-diffused layer；
4) edge of the product obtained in step 3) performs etching, and the back side carries out tying and going PSG；
5) front of the product obtained in step 4) carries out reduced passivation resisting film deposition, forms reduced passivation resisting film；
6) back side of the product obtained in step 5) carries out nano oxidized silicon growth, forms nano oxidized silicon layer；
7) back side of the product obtained in step 6) is doped boron amorphous or polysilicon deposition, forms amorphous or polycrystalline P+Layer；
8) back side of the product obtained in step 7) carries out transparent conductive film deposition, forms transparent conductive film layer；
9) front of the product obtained in step 8) uses inkjet printing mode, forms positive silver electrode；
10) back side of the product obtained in step 9) uses inkjet printing mode, forms back side silver electrode.
Preferably, in step 1), the making herbs into wool is specially：Using slot type thermokalite mode, also as alkali making herbs into wool.
Preferably, in step 2), the etching is specially：Using SF6Gas reaction ion etching, laser ablation or metal Ionic catalysis reactive mode.
Wherein, in reactive ion etching (Reactive Ion Etching, abbreviation RIE), reacting gas (such as CF4) in RF Or the decomposition that is excited in DC electric field, active particle (such as free F atom), active particle and the material reaction that is corroded are produced, Volatile materials is generated, then volatile materials is excluded into reaction chamber with aspiration pump.Reacting gas conventional RIE has SF6、CHF3、 CCl4Deng.
SF6For sulfur hexafluoride, the existing one-hundred-year history of the gas, it be two chemist Moissan and Lebeau of France in The artificial inert gas of synthesis in 1900.SF6Corrosion to silicon is mainly by SF6Dissociate caused by decomposition caused by F bases.Corrosion Volatile substances walk silicon ribbon caused by silicon, and wherein that its main function is SiF4.The pecvd silicon corrosion reaction of fluorine Spontaneous progress, it is not necessary to Ions Bombardment.Therefore it is freely fluorine-based to produce high corrosion rate, but due to being spontaneous corrosion, corrosion is outer Shape near-isotropic.
Preferably, in step 2), the matte modification is specially：Using aqueous slkali cleaning way.
Preferably, in step 4), the etching, go to tie and remove PSG (phosphorosilicate glass) specially：Using online Overwater-floating Cleaning way.
Wherein, online Overwater-floating cleaning way is：Table of the silicon chip silicon chip in corrosive solution is driven by roller Face floats, and enables silicon chip to only have the back side and edge to be contacted with solution and reacts to realize etching.
Preferably, in step 6), the nano oxidized silicon growth is specially：Using wet oxidation, ozone oxidation, hot oxygen Change, ald grows or low-pressure chemical vapor deposition mode.
Wherein, nano oxidized silicon growth refers in the silicon oxide film that silicon chip surface growth thickness is nanoscale (0~100nm) Layer；
Preferably, in step 7), the doping boron amorphous or polysilicon deposition are specially：Using low-pressure chemical vapor deposition Mode.
Wherein, amorphous or polycrystalline P+Layer means that the crystal form of this layer can be amorphous, or polycrystalline, mix Miscellaneous non-crystalline silicon and polysilicon layer can form excellent PP with silicon chip substrate+Height knot back surface field, simply after amorphous silicon layer deposition, subsequently Step can not have the pyroprocess higher than 300 degree, and polysilicon layer can have no effect on performance with high temperature resistant process.
Preferably, in step 8), the transparent conductive film deposition is specially：Using magnetron sputtering mode.
Wherein, transparent conductive film is ITO (indium oxide of tin dope three) or AZO (aluminium-doped zinc oxide).
The preparation method, nano oxidized silicon layer is formed by carrying out nano oxidized silicon growth at the back side of P-type silicon matrix, The back side doping boron amorphous or polysilicon deposition of nano oxidized silicon layer, form amorphous or polycrystalline P+Layer, in amorphous or polycrystalline P+Layer The back side carries out transparent conductive film deposition, forms transparent conductive film layer, cell backside can be provided using nano oxidized silicon layer High quality passivation, and amorphous or polycrystalline P+Layer can be used for forming tunneling structure, then coordinate transparent conductive film layer, Ke Yixian Write and improve battery back of the body passivation quality and electric current export performance, reduce back side recombination losses and electric current export loss；Further, exist The surface of P-type silicon matrix forms completely black convex-concave surface structure, recycles inkjet technology to prepare positive silver electrode by etching With back side silver electrode, so as to increase the light absorption of battery and electric current collection, reduction is optically and electrically lost, and improves crystal The conversion efficiency of silicon solar cell.
Brief description of the drawings
Fig. 1 is the structural representation of the two-sided crystal silicon solar energy battery of inkjet printing of the present invention.
In figure：1- fronts silver electrode；2- reduced passivation resisting films；3- matte texture；4- phosphorus-diffused layers；5-P type silicon substrates；6- receives Rice silicon oxide layer；7- amorphous or polycrystalline p+ layers；8- transparent conductive film layers；9- back sides silver electrode.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
As shown in figure 1, a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix 5, the P-type silicon base The front of body 5 is provided with phosphorus-diffused layer 4, and the front of the phosphorus-diffused layer 4 is provided with matte texture 3, and the matte texture 3 is just Face is provided with reduced passivation resisting film 2, and the front of the reduced passivation resisting film 2 is provided with positive silver electrode 1；The back of the body of the P-type silicon matrix 5 Face is provided with nano oxidized silicon layer 6, and the back side of the nano oxidized silicon layer 6 is provided with amorphous or polycrystalline P+Layer 7, the amorphous or Polycrystalline P+The back side of layer 7 is provided with transparent conductive film layer 8, and the back side of the transparent conductive film layer 8 is provided with back silver electricity Pole 9.
A kind of preparation method of the two-sided crystal silicon solar energy battery of inkjet printing, comprises the following steps：
1) damaging layer on the surface of P-type silicon matrix 5 and making herbs into wool are removed；Wherein, in step 1), the making herbs into wool is specially：Using Slot type thermokalite mode.
Specifically, selecting 156mm p type single crystal silicon piece, its resistivity is 1 Ω cm as P-type silicon matrix 5.
After going damage to P-type silicon matrix 5, with mass concentration fraction be 0.5% sodium hydroxide or potassium hydroxide solution, At 75 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, prepares the matte of Pyramid, then with mass concentration point The hydrofluoric acid that number is 1% carries out cleaning and goes the removal of impurity.
2) surface of the product obtained in step 1) performs etching, and forms completely black convex-concave surface structure, and carry out matte Modification, form matte texture 3；
Wherein, in step 2), the etching is specially：Using SF6Gas, utilize reactive ion etching mode；Specifically, Using the method for reactive ion etching, SF is used6Gas forms plasma and reacted with silicon chip surface, is formed and received in existing matte The matte texture 3 of meter level, the surface of the matte texture 3 is rough structure, and surface can be shown completely black when being reflected so as to light.
Wherein, the matte, which is modified, is specially：Using aqueous slkali cleaning way；Specifically, use quality concentration fraction is 0.5% sodium hydroxide or potassium hydroxide solution, at 25 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, modifies table Face Porous Silicon structures, reduce surface defect.
3) surface of the product obtained in step 2) carries out phosphorus diffusion knot, forms phosphorus-diffused layer 4；
Specifically, by tubular type high temperature thermal diffusion mode, using POCl3Phosphorus diffusion, formation side are carried out to the front of silicon chip Hinder for 95 Ω/sq N-type layer；
Wherein, POCl3It is a kind of industrial chemicals for POCl3, is water white transparency, there is the liquid of pungent odour Body, the violent smoke in humid air, is hydrolyzed into phosphoric acid and hydrogen chloride, further generates HP2O4Cl3。
4) edge of the product obtained in step 3) performs etching, and the back side carries out tying and going PSG；
Wherein, in step 4), the etching, go to tie and go the PSG to be specially：Using online Overwater-floating cleaning way.Tool Body, back side phosphorosilicate glass (PSG) is removed (although only existing using wet method in line equipment (that is, online roller type equipment) The front of silicon chip carries out phosphorus diffusion and forms phosphorosilicate glass, but phosphorosilicate glass can penetrate into the back side of silicon chip), realize that the back side is thrown Light, front phosphorosilicate glass is then removed, then use mass concentration fraction to be cleaned for 5% hydrofluoric acid solution.
5) front of the product obtained in step 4) carries out reduced passivation resisting film 2 and deposited, and forms reduced passivation resisting film 2；Wherein, The reduced passivation resisting film 2 is SiNx passivating films；
Specifically, the method grown silicon nitride in the front of P-type silicon matrix 5 with PECVD (plasma chemical vapor deposition) Antireflective film, the thickness of passivated reflection reducing membrane is 80nm.
6) back side of the product obtained in step 5) carries out nano oxidized silicon growth, forms nano oxidized silicon layer 6；Its In, in step 6), the nano oxidized silicon growth is specially：Using wet oxidation mode.Specifically, the nano oxidized silicon layer 6 thickness is 1.2nm.
7) back side of the product obtained in step 6) is doped boron amorphous or polysilicon deposition, forms amorphous or polycrystalline P+Layer 7；Wherein, in step 6), the doping boron amorphous or polysilicon deposition are specially：Using low-pressure chemical vapor deposition (LPCVD) mode；Preferably, the crystal form of amorphous or polycrystalline p+ layers 7 is polycrystalline form, amorphous or the polycrystalline P+Layer 7 Thickness is 40nm, and doping concentration is 3 × 1020cm-3。
8) back side of the product obtained in step 7) carries out transparent conductive film deposition, forms transparent conductive film layer 8；
Wherein, in step 8), the transparent conductive film deposition is specially：Using magnetron sputtering mode.
Preferably, the thickness of the transparent conductive film layer 8 is 100nm.
9) front of the product obtained in step 8) uses inkjet printing mode, forms positive silver electrode 1；
10) back side of the product obtained in step 9) uses inkjet printing mode, forms back side silver electrode 9.
Specifically, by being dried after inkjet printing backplate and thin grid line, then inkjet printing front electrode and thin grid Line.
Finally sinter, test, the two-sided crystal silicon solar energy battery of inkjet printing may finally be formed.
In the embodiment, battery conversion efficiency batch average efficiency reaches 22.3%, and optical attenuation, front main grid, the back side Electrode and Al-BSF pulling force, and assembly end reliability testing meet TUV standards.
Embodiment 2
As shown in figure 1, a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix 5, the P-type silicon base The front of body 5 is provided with phosphorus-diffused layer 4, and the front of the phosphorus-diffused layer 4 is provided with matte texture 3, and the matte texture 3 is just Face is provided with reduced passivation resisting film 2, and the front of the reduced passivation resisting film 2 is provided with positive silver electrode 1；The back of the body of the P-type silicon matrix 5 Face is provided with nano oxidized silicon layer 6, and the back side of the nano oxidized silicon layer 6 is provided with amorphous or polycrystalline P+Layer 7, the amorphous or Polycrystalline P+The back side of layer 7 is provided with transparent conductive film layer 8, and the back side of the transparent conductive film layer 8 is provided with back silver electricity Pole 9.
A kind of preparation method of the two-sided crystal silicon solar energy battery of inkjet printing, comprises the following steps：
1) damaging layer on the surface of P-type silicon matrix 5 and making herbs into wool are removed；Wherein, in step 1), the making herbs into wool is specially：Using Slot type thermokalite mode.
Specifically, selecting 156mm p type single crystal silicon piece, its resistivity is 1 Ω cm as P-type silicon matrix 5.
After going damage to P-type silicon matrix 5, with mass concentration fraction be 0.5% sodium hydroxide or potassium hydroxide solution, At 75 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, prepares the matte of Pyramid, then with mass concentration point The hydrofluoric acid that number is 1% carries out cleaning and goes the removal of impurity.
2) surface of the product obtained in step 1) performs etching, and forms completely black convex-concave surface structure, and carry out matte Modification, form matte texture 3；
Wherein, in step 2), the etching is specially：Utilize metal ion catalysis reactive mode；Specifically, using metal The method of ionic catalysis reaction, using silver nitrate solution and silicon chip surface reaction production nano-Ag particles, passing through HF/HNO3It is mixed Close solution is having matte to form nano level matte texture 3 under the catalysis of nano surface Argent grain, and the surface of the matte texture 3 is Rough structure, surface can be shown completely black when being reflected so as to light.
Wherein, the matte, which is modified, is specially：Using aqueous slkali cleaning way；Specifically, use quality concentration fraction is 0.5% sodium hydroxide or potassium hydroxide solution, at 25 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, modifies table Face Porous Silicon structures, reduce surface defect.
3) surface of the product obtained in step 2) carries out phosphorus diffusion knot, forms phosphorus-diffused layer 4；
Specifically, by tubular type high temperature thermal diffusion mode, using POCl3Phosphorus diffusion, formation side are carried out to the front of silicon chip Hinder for 100 Ω/sq N-type layer；
Wherein, POCl3It is a kind of industrial chemicals for POCl3, is water white transparency, there is the liquid of pungent odour Body, the violent smoke in humid air, is hydrolyzed into phosphoric acid and hydrogen chloride, further generates HP2O4Cl3。
4) edge of the product obtained in step 3) performs etching, and the back side carries out tying and going PSG；
Wherein, in step 4), the etching, go to tie and go the PSG to be specially：Using online Overwater-floating cleaning way.Tool Body, back side phosphorosilicate glass (PSG) is removed (although only existing using wet method in line equipment (that is, online roller type equipment) The front of silicon chip carries out phosphorus diffusion and forms phosphorosilicate glass, but phosphorosilicate glass can penetrate into the back side of silicon chip), realize that the back side is thrown Light, front phosphorosilicate glass is then removed, then use mass concentration fraction to be cleaned for 5% hydrofluoric acid solution.
5) front of the product obtained in step 4) carries out reduced passivation resisting film 2 and deposited, and forms reduced passivation resisting film 2；Wherein, The reduced passivation resisting film 2 is SiO2/ SiNx overlayer passivation films；
Specifically, the method grown silicon nitride in the front of P-type silicon matrix 5 with PECVD (plasma chemical vapor deposition) Antireflective film, the thickness of passivated reflection reducing membrane is 80nm.
6) back side of the product obtained in step 5) carries out nano oxidized silicon growth, forms nano oxidized silicon layer 6；Its In, in step 6), the nano oxidized silicon growth is specially：Using ALD (ald growth) mode.Specifically, it is described The thickness of nano oxidized silicon layer 6 is 1.3nm.
7) back side of the product obtained in step 6) is doped boron amorphous or polysilicon deposition, forms amorphous or polycrystalline P+Layer 7；Wherein, in step 7), the doping boron amorphous or polysilicon deposition are specially：Using low-pressure chemical vapor deposition (LPCVD) mode；Preferably, amorphous or polycrystalline P+The crystal form of layer 7 is amorphous form, amorphous or the polycrystalline P+The thickness of layer 7 Spend for 40nm, doping concentration 1020cm-3。
8) back side of the product obtained in step 7) carries out transparent conductive film deposition, forms transparent conductive film layer 8；
Wherein, in step 8), the transparent conductive film deposition is specially：Using magnetron sputtering mode.
Preferably, the thickness of the transparent conductive film layer 8 is 100nm.
9) front of the product obtained in step 8) uses inkjet printing mode, forms positive silver electrode 1；
10) back side of the product obtained in step 9) uses inkjet printing mode, forms back side silver electrode 9.
Specifically, by being dried after inkjet printing backplate and thin grid line, then inkjet printing front electrode and thin grid Line.
Finally sinter, test, the two-sided crystal silicon solar energy battery of inkjet printing may finally be formed.
In the embodiment, battery conversion efficiency batch average efficiency reaches 21.1%, and optical attenuation, front main grid, the back side Electrode and Al-BSF pulling force, and assembly end reliability testing meet TUV standards.
Embodiment 3
As shown in figure 1, a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix 5, the P-type silicon base The front of body 5 is provided with phosphorus-diffused layer 4, and the front of the phosphorus-diffused layer 4 is provided with matte texture 3, and the matte texture 3 is just Face is provided with reduced passivation resisting film 2, and the front of the reduced passivation resisting film 2 is provided with positive silver electrode 1；The back of the body of the P-type silicon matrix 5 Face is provided with nano oxidized silicon layer 6, and the back side of the nano oxidized silicon layer 6 is provided with amorphous or polycrystalline P+Layer 7, the amorphous or Polycrystalline P+The back side of layer 7 is provided with transparent conductive film layer 8, and the back side of the transparent conductive film layer 8 is provided with back silver electricity Pole 9.
A kind of preparation method of the two-sided crystal silicon solar energy battery of inkjet printing, comprises the following steps：
1) damaging layer on the surface of P-type silicon matrix 5 and making herbs into wool are removed；Wherein, in step 1), the making herbs into wool is specially：Using Slot type thermokalite mode.
Specifically, selecting 156mm p type single crystal silicon piece, its resistivity is 1 Ω cm as P-type silicon matrix 5.
After going damage to P-type silicon matrix 5, with mass concentration fraction be 0.5% sodium hydroxide or potassium hydroxide solution, At 75 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, prepares the matte of Pyramid, then with mass concentration point The hydrofluoric acid that number is 1% carries out cleaning and goes the removal of impurity.
2) surface of the product obtained in step 1) performs etching, and forms completely black convex-concave surface structure, and carry out matte Modification, form matte texture 3；
Wherein, in step 2), the etching is specially：Using SF6Gas, utilize RIE (reactive ion etching) reaction side Formula；Specifically, the method reacted using RIE, uses SF6Gas forms plasma and reacted with silicon chip surface, in existing matte Nano level matte texture 3 is formed, the surface of the matte texture 3 is rough structure, so as to which surface can show during light reflection Show completely black.
Wherein, the matte, which is modified, is specially：Using aqueous slkali cleaning way；Specifically, use quality concentration fraction is 0.5% sodium hydroxide or potassium hydroxide solution, at 25 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, modifies table Face Porous Silicon structures, reduce surface defect.
3) surface of the product obtained in step 2) carries out phosphorus diffusion knot, forms phosphorus-diffused layer 4；
Specifically, by tubular type high temperature thermal diffusion mode, using POCl3Phosphorus diffusion, formation side are carried out to the front of silicon chip Hinder for 110 Ω/sq N-type layer；
Wherein, POCl3It is a kind of industrial chemicals for POCl3, is water white transparency, there is the liquid of pungent odour Body, the violent smoke in humid air, is hydrolyzed into phosphoric acid and hydrogen chloride, further generates HP2O4Cl3。
4) edge of the product obtained in step 3) performs etching, and the back side carries out tying and going PSG；
Wherein, in step 4), the etching, go to tie and go the PSG to be specially：Using online Overwater-floating cleaning way.Tool Body, back side phosphorosilicate glass (PSG) is removed (although only existing using wet method in line equipment (that is, online roller type equipment) The front of silicon chip carries out phosphorus diffusion and forms phosphorosilicate glass, but phosphorosilicate glass can penetrate into the back side of silicon chip), realize that the back side is thrown Light, front phosphorosilicate glass is then removed, then use mass concentration fraction to be cleaned for 5% hydrofluoric acid solution.
5) front of the product obtained in step 4) carries out reduced passivation resisting film 2 and deposited, and forms reduced passivation resisting film 2；Wherein, The reduced passivation resisting film 2 is SiO2/ SiNx overlayer passivation films；
Specifically, the method grown silicon nitride in the front of P-type silicon matrix 5 with PECVD (plasma chemical vapor deposition) Antireflective film, the thickness of passivated reflection reducing membrane is 80nm.
6) back side of the product obtained in step 5) carries out nano oxidized silicon growth, forms nano oxidized silicon layer 6；Its In, in step 6), the nano oxidized silicon growth is specially：Using wet oxidation mode.Specifically, the nano oxidized silicon layer 6 thickness is 1.2nm.
7) back side of the product obtained in step 6) is doped boron amorphous or polysilicon deposition, forms amorphous or polycrystalline P+Layer 7；Wherein, in step 7), the doping boron amorphous or polysilicon deposition are specially：Using low-pressure chemical vapor deposition (LPCVD) mode；Preferably, amorphous or polycrystalline P+The crystal form of layer 7 is polycrystalline form, amorphous or polycrystalline the p+ layers 7 Thickness is 50nm, and doping concentration is 5 × 1020cm-3。
8) back side of the product obtained in step 7) carries out transparent conductive film deposition, forms transparent conductive film layer 8；
Wherein, in step 8), the transparent conductive film deposition is specially：Using magnetron sputtering mode.
Preferably, the thickness of the transparent conductive film layer 8 is 100nm.
9) front of the product obtained in step 8) uses inkjet printing mode, forms positive silver electrode 1；
10) back side of the product obtained in step 9) uses inkjet printing mode, forms back side silver electrode 9.
Specifically, by being dried after inkjet printing backplate and thin grid line, then inkjet printing front electrode and thin grid Line.
Finally sinter, test, the two-sided crystal silicon solar energy battery of inkjet printing may finally be formed.
In the embodiment, battery conversion efficiency batch average efficiency reaches 21.2%, and optical attenuation, front main grid, the back side Electrode and Al-BSF pulling force, and assembly end reliability testing meet TUV standards.
Embodiment 4
As shown in figure 1, a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix 5, the P-type silicon base The front of body 5 is provided with phosphorus-diffused layer 4, and the front of the phosphorus-diffused layer 4 is provided with matte texture 3, and the matte texture 3 is just Face is provided with reduced passivation resisting film 2, and the front of the reduced passivation resisting film 2 is provided with positive silver electrode 1；The back of the body of the P-type silicon matrix 5 Face is provided with nano oxidized silicon layer 6, and the back side of the nano oxidized silicon layer 6 is provided with amorphous or polycrystalline P+Layer 7, the amorphous or Polycrystalline P+The back side of layer 7 is provided with transparent conductive film layer 8, and the back side of the transparent conductive film layer 8 is provided with back silver electricity Pole 9.
A kind of preparation method of the two-sided crystal silicon solar energy battery of inkjet printing, comprises the following steps：
1) damaging layer on the surface of P-type silicon matrix 5 and making herbs into wool are removed；Wherein, in step 1), the making herbs into wool is specially：Using Slot type thermokalite mode.
Specifically, selecting 156mm p type single crystal silicon piece, its resistivity is 1 Ω cm as P-type silicon matrix 5.
After going damage to P-type silicon matrix 5, with mass concentration fraction be 0.5% sodium hydroxide or potassium hydroxide solution, At 75 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, prepares the matte of Pyramid, then with mass concentration point The hydrofluoric acid that number is 1% carries out cleaning and goes the removal of impurity.
2) surface of the product obtained in step 1) performs etching, and forms completely black convex-concave surface structure, and carry out matte Modification, form matte texture 3；
Wherein, in step 2), the etching is specially：Using SF6Gas, utilize RIE reactive modes；Specifically, use The method of RIE etchings, uses SF6Gas forms plasma and reacted with silicon chip surface, and nano level suede is formed in existing matte Plane texture 3, the surface of the matte texture 3 is rough structure, and surface can be shown completely black when being reflected so as to light.
Wherein, the matte, which is modified, is specially：Using aqueous slkali cleaning way；Specifically, use quality concentration fraction is 0.5% sodium hydroxide or potassium hydroxide solution, at 25 DEG C, chemical attack is carried out to the surface of P-type silicon matrix 5, modifies table Face Porous Silicon structures, reduce surface defect.
3) surface of the product obtained in step 2) carries out phosphorus diffusion knot, forms phosphorus-diffused layer 4；
Specifically, by tubular type high temperature thermal diffusion mode, using POCl3Phosphorus diffusion, formation side are carried out to the front of silicon chip Hinder for 120 Ω/sq N-type layer；
Wherein, POCl3It is a kind of industrial chemicals for POCl3, is water white transparency, there is the liquid of pungent odour Body, the violent smoke in humid air, is hydrolyzed into phosphoric acid and hydrogen chloride, further generates HP2O4Cl3。
4) edge of the product obtained in step 3) performs etching, and the back side carries out tying and going PSG；
Wherein, in step 4), the etching, go to tie and go the PSG to be specially：Using online Overwater-floating cleaning way.Tool Body, back side phosphorosilicate glass (PSG) is removed (although only existing using wet method in line equipment (that is, online roller type equipment) The front of silicon chip carries out phosphorus diffusion and forms phosphorosilicate glass, but phosphorosilicate glass can penetrate into the back side of silicon chip), realize that the back side is thrown Light, front phosphorosilicate glass is then removed, then use mass concentration fraction to be cleaned for 5% hydrofluoric acid solution.
5) front of the product obtained in step 4) carries out reduced passivation resisting film 2 and deposited, and forms reduced passivation resisting film 2；Wherein, The reduced passivation resisting film 2 is SiO2/ SiNx overlayer passivation films；
Specifically, the method grown silicon nitride in the front of P-type silicon matrix 5 with PECVD (plasma chemical vapor deposition) Antireflective film, the thickness of passivated reflection reducing membrane is 80nm.
6) back side of the product obtained in step 5) carries out nano oxidized silicon growth, forms nano oxidized silicon layer 6；Its In, in step 6), the nano oxidized silicon growth is specially：Using LPCVD depositional modes.Specifically, the nano silicon oxide The thickness of layer 6 is 1.2nm.
7) back side of the product obtained in step 6) is doped boron amorphous or polysilicon deposition, forms amorphous or polycrystalline P+Layer 7；Wherein, in step 7), the doping boron amorphous or polysilicon deposition are specially：Using low-pressure chemical vapor deposition (LPCVD) mode；Preferably, amorphous or polycrystalline P+The crystal form of layer 7 is 10nm amorphous and 40nm polycrystalline forms, the amorphous Or polycrystalline P+The combination thickness of layer 7 is 50nm, and doping concentration is 8 × 1020cm-3。
8) back side of the product obtained in step 7) carries out transparent conductive film deposition, forms transparent conductive film layer 8；
Wherein, in step 8), the transparent conductive film deposition is specially：Using magnetron sputtering mode.
Preferably, the thickness of the transparent conductive film layer 8 is 100nm.
9) front of the product obtained in step 8) uses inkjet printing mode, forms positive silver electrode 1；
10) back side of the product obtained in step 9) uses inkjet printing mode, forms back side silver electrode 9.
Specifically, by being dried after inkjet printing backplate and thin grid line, then inkjet printing front electrode and thin grid Line.
Finally sinter, test, the two-sided crystal silicon solar energy battery of inkjet printing may finally be formed.
In the embodiment, battery conversion efficiency batch average efficiency reaches 22.15%, and optical attenuation, front main grid, the back side Electrode and Al-BSF pulling force, and assembly end reliability testing meet TUV standards.
Comparative example 1
Typical inkjet prints the preparation method of two-sided crystal silicon solar energy battery, comprises the following steps：
1) damaging layer and the making herbs into wool of P-type silicon matrix surface are removed；
2) back surface of the product obtained in step 1) carries out boron diffusion, forms diffused layer of boron；
Specifically, by tubular type high temperature thermal diffusion mode, using BBr3Boron diffusion is carried out to the back side of silicon chip, forms sheet resistance For 40 Ω/sq P+Type layer；
3) front of the product obtained in step 2) carries out one side and goes to tie；
Wherein, it is described to go the knot to be specially in step 3)：Using online roller band liquid cleaning way.Specifically, use is wet Method in line equipment (that is, online roller type equipment) removes front Pyrex (BSG).
5) front of the product obtained in step 4) carries out phosphorus diffusion knot, forms phosphorus doping layer；
Specifically, by tubular type high temperature thermal diffusion mode, using POCl3Phosphorus diffusion, formation side are carried out to the front of silicon chip Hinder for 100 Ω/sq N-type layer.
6) product obtained in step 5) carries out etching edge and BSG and PSG is removed；
Specifically, using online Overwater-floating cleaning way.Specifically, using wet method in line equipment (that is, online Roller type equipment) remove flash trimming knot, front phosphorosilicate glass (PSG) and back side Pyrex (BSG).
7) the two-sided carry out nitride deposition of the product obtained in step 6), thickness 80nm；
8) front of the product obtained in step 7) prepares positive silver electrode；
9) back side of the product obtained in step 8) prepares back side silver electrode.
Finally sinter, test, ultimately form two-sided crystal silicon solar energy battery.
In this preparation method, battery conversion efficiency batch average efficiency is only 20.1%, and it is obvious not as the present invention Preparation method battery conversion efficiency batch average efficiency.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (10)

1. a kind of two-sided crystal silicon solar energy battery of inkjet printing, including P-type silicon matrix, it is characterised in that the P-type silicon matrix Front be provided with phosphorus-diffused layer, the front of the phosphorus-diffused layer is provided with matte texture, the front setting of the matte texture There is reduced passivation resisting film, the front of the reduced passivation resisting film is provided with positive silver electrode；
The back side of the P-type silicon matrix is provided with nano oxidized silicon layer, the back side of the nano oxidized silicon layer be provided with amorphous or Polycrystalline P+Layer, amorphous or the polycrystalline P+The back side of layer is provided with transparent conductive film layer, the back side of the transparent conductive film layer It is provided with back side silver electrode.
2. the two-sided crystal silicon solar energy battery of inkjet printing according to claim 1, it is characterised in that the P-type silicon base Body is p-type silicon chip, and its resistivity is 0.5-6 Ω cm；
The reduced passivation resisting film is SiNx passivating films or SiO2/ SiNx overlayer passivation films.
3. the two-sided crystal silicon solar energy battery of inkjet printing according to claim 1, it is characterised in that described nano oxidized The thickness of silicon layer is 0.3-5nm；
Amorphous or the polycrystalline P+The thickness of layer is 10-1000nm, doping concentration 1017~1022cm-3；
The thickness of the transparent conductive film layer is 10-500nm.
4. a kind of preparation method of two-sided crystal silicon solar energy battery of inkjet printing as described in claim any one of 1-3, its It is characterised by, comprises the following steps：
1) damaging layer and the making herbs into wool of P-type silicon matrix surface are removed；
2) surface of the product obtained in step 1) performs etching, and forms completely black convex-concave surface structure, and carries out matte modification, Form matte texture；
3) surface of the product obtained in step 2) carries out phosphorus diffusion knot, forms phosphorus-diffused layer；
4) edge of the product obtained in step 3) performs etching, and the back side carries out tying and going PSG；
5) front of the product obtained in step 4) carries out reduced passivation resisting film deposition, forms reduced passivation resisting film；
6) back side of the product obtained in step 5) carries out nano oxidized silicon growth, forms nano oxidized silicon layer；
7) back side of the product obtained in step 6) is doped boron amorphous or polysilicon deposition, forms amorphous or polycrystalline P+Layer；
8) back side of the product obtained in step 7) carries out transparent conductive film deposition, forms transparent conductive film layer；
9) front of the product obtained in step 8) uses inkjet printing mode, forms positive silver electrode；
10) back side of the product obtained in step 9) uses inkjet printing mode, forms back side silver electrode.
5. preparation method according to claim 4, it is characterised in that in step 1), the making herbs into wool is specially：Using slot type Thermokalite mode.
6. preparation method according to claim 4, it is characterised in that in step 2), the etching is specially：Using SF6Gas Reactive ion etching, laser ablation or the metal ion catalysis reactive mode of body；
The matte is modified：Using aqueous slkali cleaning way.
7. preparation method according to claim 4, it is characterised in that in step 4), the etching, go to tie and go PSG to have Body is：Using online Overwater-floating cleaning way.
8. preparation method according to claim 4, it is characterised in that in step 6), the nano oxidized silicon growth is specific For：Using wet oxidation, ozone oxidation, thermal oxide, ald growth or low-pressure chemical vapor deposition mode.
9. preparation method according to claim 4, it is characterised in that in step 7), the doping boron amorphous or polysilicon Deposition is specially：Using low-pressure chemical vapor deposition mode.
10. preparation method according to claim 4, it is characterised in that in step 8), the transparent conductive film deposition tool Body is：Using magnetron sputtering mode.
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CN104795127A (en) * 2015-03-30 2015-07-22 无锡帝科电子材料科技有限公司 Electric conduction slurry and application of electric conduction slurry in N type silicon wafer solar cells

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