CN106159022B - A kind of crystal silicon solar cell sheet and preparation method thereof - Google Patents
A kind of crystal silicon solar cell sheet and preparation method thereof Download PDFInfo
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Abstract
To lift the photoelectric transformation efficiency of crystal silicon solar cell sheet, the invention provides a kind of crystal silicon solar cell sheet, including silicon substrate, the shady face of the silicon substrate is sequentially provided with conducting medium layer, protective layer and shady face gate electrode line；The conducting medium layer contacts with the silicon substrate；Al-BSF is additionally provided between silicon substrate and the shady face gate electrode line, the Al-BSF runs through the conducting medium layer and protective layer, and is contacted simultaneously with silicon substrate, conducting medium layer and shady face gate electrode line；The conducting medium layer material is p-type zinc oxide, and the silicon substrate is p-type polycrystalline silicon silicon substrate.Meanwhile the invention also discloses the preparation method of above-mentioned crystal silicon solar cell sheet.The photoelectric transformation efficiency of crystal silicon solar cell sheet provided by the invention is high.
Description
Technical field
The present invention relates to a kind of crystal silicon solar cell sheet and preparation method thereof.
Background technology
With the development and intensified competition of solar energy industry, client is to the efficiency requirements more and more higher of solar cell, OK
Industry access threshold is also improving, it is therefore desirable to explores the lifting that more industrialization technologies realize conversion efficiency of solar cell.Mesh
Preceding solar cell phototropic face technology is very ripe, and the focus for lifting conversion efficiency is increasingly turned to as with very big potentiality
The back side.By ald (ALD) technology, the back of the body passivation cell of backside deposition alumina passivation layer is previous bright as mesh
Point.Passivated emitter and back surface passivation battery (PERC) are based primarily upon aluminum oxide for the good passivation effect of P-type silicon piece, can
To be obviously improved the Isc of solar cell and Voc, so as to raising efficiency.
It is typically as follows to be currently based on the technological process of the back of the body passivating solar battery (PERC) of p-type polysilicon silicon substrate, is carving
It is preceding identical with conventional crystalline silion cell to lose process (including the process), after etching, using technique for atomic layer deposition (ALD) in silicon chip
Shady face deposited oxide aluminium film passivation layer, then annealed, then phototropic face plate SiNx as antireflective coating, then exist again
On the alumina passivation layer of shady face, plating layer of sin x films, then using laser grooving, are republished after cutting and led as protective layer
Plasma-based material, the printing of slurry is similar with sintering process with conventional batteries, i.e., first prints back silver paste in shady face, then in back silver paste
Back field aluminum paste is printed in remaining region, then prints positive silver paste in phototropic face, obtains carrying on the back crystalline silicon solar cell with passivation piece after sintering.
After the shady face deposition of aluminium oxide and silicon nitride layer of silicon chip, because aluminum oxide and silicon nitride layer are all the bad of electricity
Conductor, aluminium paste sintering is set to be contacted with back side silicon to form the passage of photo-generated carrier even if using the method for laser grooving, but because
The area of laser grooving is small, the lateral transport poor performance of photo-generated carrier, causes the series resistance of battery to increase, under fill factor, curve factor
Drop.On the other hand, it is necessary to use higher temperature to be annealed to the passivation layer of deposition to carry after alumina passivation layer is prepared
The effect of passivation layer is risen, in the process, the high-temperature annealing process of long period, the increasing of defect concentration in silicon chip may be caused
Add.Also, use and aluminium paste is printed in the entire area of silicon nitride protective layer, after sintering, in the part of laser unslotted, aluminium paste
In glass dust in the molten state, may successively corrode and penetrate silicon nitride and alumina layer, cause aluminium paste to passivation layer
Destruction, so as to a certain extent, weaken lifting effect of the passivation layer to cell photoelectric performance.
The content of the invention
The technical problems to be solved by the invention are to lift the photoelectric transformation efficiency of crystal silicon solar cell sheet, there is provided one
Kind crystal silicon solar cell sheet.
Technical scheme is as follows used by the present invention solves above-mentioned technical problem：
A kind of crystal silicon solar cell sheet, including silicon substrate are provided, the shady face of the silicon substrate is sequentially provided with conduction
Dielectric layer, protective layer and shady face gate electrode line；The conducting medium layer contacts with the silicon substrate；The silicon substrate and backlight
It is additionally provided with Al-BSF between the gate electrode line of face, the Al-BSF runs through the conducting medium layer and protective layer, and simultaneously and silicon
Matrix, conducting medium layer and the contact of shady face gate electrode line；The conducting medium layer material is p-type zinc oxide, the silicon substrate
For p-type polycrystalline silicon silicon substrate.
Meanwhile present invention also offers the preparation method of above-mentioned crystal silicon solar cell sheet, comprise the following steps：
S1, the silicon substrate on phototropic face with diffusion layer is provided, the silicon substrate is p-type polycrystalline silicon silicon substrate, in silicon
The shady face deposition p-type zinc oxide of matrix, forms conducting medium layer；
S2, protective layer is prepared on the conducting medium layer, then prepare Al-BSF on the protection layer, the Al-BSF is passed through
The conducting medium layer and protective layer are worn, and is contacted simultaneously with silicon substrate, conducting medium layer；
S3, the shady face gate electrode line contacted with the Al-BSF is prepared on the protective layer of silicon substrate shady face, in silicon
The phototropic face gate electrode line contacted with diffusion layer is prepared on matrix phototropic face.
In crystal silicon solar cell sheet provided by the invention, p-type polycrystalline silicon silicon substrate and p-type zinc oxide conducting medium
Layer forms PP+ hetero-junctions, and the hetero-junctions has the function that to collect photo-generated carrier, therefore the open-circuit voltage of cell piece simultaneously
(Voc) it is significantly improved, the series resistance (Rs) of cell piece is also improved compared with back of the body passivation cell (PERC).Meanwhile
The conducting medium layer also has certain passivation effect to silicon silicon substrate surface, adds light path to a certain extent, increases
Absorption of the silicon silicon substrate to long wave, therefore the short circuit current (Isc) of cell piece is also improved.
Brief description of the drawings
Fig. 1 is the phototropic face front view of crystal silicon solar cell sheet prepared by the embodiment of the present invention 1；
Fig. 2 be in Fig. 1 A-A to sectional view；
Fig. 3 is the shady face front view of crystal silicon solar cell sheet prepared by the embodiment of the present invention 1.
Reference in Figure of description is as follows：
1st, phototropic face electrode main grid line；2nd, phototropic face electrode pair grid line；3rd, antireflective coating；4th, diffusion layer；5th, silicon substrate；6、
Conducting medium layer；7th, protective layer；8th, Al-BSF；9th, shady face gate electrode line.
Embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect are more clearly understood, below in conjunction with
Drawings and Examples, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used
To explain the present invention, it is not intended to limit the present invention.
Crystal silicon solar cell sheet provided by the invention, including silicon substrate, the shady face of the silicon substrate are sequentially provided with
Conducting medium layer, protective layer and shady face gate electrode line；The conducting medium layer contacts with the silicon substrate；The silicon substrate and
Al-BSF is additionally provided between shady face gate electrode line, the Al-BSF runs through the conducting medium layer and protective layer, and simultaneously
Contacted with silicon substrate, conducting medium layer and shady face gate electrode line；The conducting medium layer material is p-type zinc oxide, the silicon
Matrix is p-type polycrystalline silicon silicon substrate.
In the present invention, the structure on silicon substrate and silicon substrate phototropic face can use existing structure, for example, the silicon substrate
Phototropic face on there is diffusion layer and phototropic face gate electrode line successively.
As existing, phototropic face gate electrode line generally includes orthogonal phototropic face electrode main grid line and phototropic face electrode
Secondary grid line.Wherein, phototropic face electrode main grid line is thicker, negligible amounts.Phototropic face electrode pair grid line is thinner, and quantity is more.And
It is parallel to each other between multiple phototropic face electrode main grid lines, is parallel to each other between multiple phototropic face electrode pair grid lines.
Generally, also there is antireflection layer on the diffusion layer.The thickness of conventional antireflection layer is 70-80nm, its material
Usually silicon nitride.
Now, phototropic face gate electrode line is located on the antireflection layer.
Present invention focuses on the improvement to crystal silicon solar cell sheet shady face structure.Specifically, the silicon substrate
Shady face on there is conducting medium layer.In the present invention, the conducting medium layer material is p-type zinc oxide.
According to the present invention, p-type polycrystalline silicon silicon substrate forms PP+ hetero-junctions with p-type zinc oxide conducting medium layer, and this is heterogeneous
Knot has the function that to collect photo-generated carrier simultaneously, therefore the open-circuit voltage (Voc) of cell piece is significantly improved, cell piece
Series resistance (Rs) is also improved compared with back of the body passivation cell (PERC).Meanwhile the conducting medium layer is to silicon silicon substrate surface
Also there is certain passivation effect, add light path to a certain extent, increase absorption of the silicon silicon substrate to long wave, therefore electricity
The short circuit current (Isc) of pond piece is also improved.
For aforementioned p-type zinc oxide conducting medium layer, to be further beneficial to the photoelectricity for improving crystal silicon solar cell sheet
Conversion efficiency, under preferable case, the thickness of the conducting medium layer is 10-100nm；More preferably 20-50nm.
Meanwhile when the film resiativity of the conducting medium layer is 0.01-0.1 Ω cm, more conducively improve crystalline silicon too
The open-circuit voltage of positive energy cell piece.
Such as routine, the shady face of the silicon substrate also has protective layer, shady face gate electrode line and Al-BSF.With it is existing
Back of the body passivation solar cell chip architecture is similar, and the Al-BSF runs through the conducting medium layer and protective layer, and simultaneously and silicon substrate
Body, conducting medium layer and the contact of shady face gate electrode line.
Above-mentioned protective layer is directly covered with above-mentioned conducting medium layer, being protected to it.In this area, conventional protection
The material of layer is silicon nitride.In the present invention, the thickness of the protective layer is preferably 50-300nm.
As previously described, because nitridation silicon resistivity is higher, on the other hand, in the present invention, the protective layer is provided with the first groove,
First groove is extended on silicon substrate through conducting medium layer.The Al-BSF is at least filled in first groove.
Now, Al-BSF contacts through above-mentioned first groove with silicon substrate, you can realizes that the structure of silicon nitride both sides is mutual
Conducting.Under preferable case, the Al-BSF is only located in first groove.
In the case of, according to the invention it is preferred to, the protective layer is provided with multiple first grooves being parallel to each other.
The for the benefit of lifting of the silicon chip minority carrier life of passivation layer, while the formation beneficial to Al-BSF and the receipts of photogenerated current
Collection, in of the invention, under preferable case, the width w of first groove1For 0.5-5mm, the length side of two neighboring first groove
To the distance between center line c be 5-10mm.In the case of more preferably, the width w of first groove1For 1-2mm, adjacent two
The distance between the center line of length direction of individual first groove c is 6-8mm.
Meanwhile for the first groove, under preferable case, the end in the first groove length direction and the silicon substrate edge
Distance δ1For 2-5mm.
Al-BSF can be effectively formed by above-mentioned first groove.As existing, on the basis of Al-BSF, the silicon substrate back of the body
Shady face gate electrode line is should also have in smooth surface.In the present invention, specifically, the shady face gate electrode line and first groove
Vertically；The width w of the shady face gate electrode line2For 2-5mm, the end of the shady face gate electrode line length direction with it is described
The distance δ at silicon substrate edge2For 2-5mm.
As it is known in the art, above-mentioned Al-BSF material is usually aluminium, can be prepared by aluminium paste is sintered, and it is above-mentioned
The phototropic face gate electrode line of shady face gate electrode line and silicon substrate phototropic face (phototropic face electrode main grid line and phototropic face electrode pair
Grid line) material be usually silver, can be prepared by the way that silver paste is sintered.
The preparation method of above-mentioned crystal silicon solar cell sheet is additionally provided in the present invention, is specifically comprised the following steps：
S1, the silicon substrate on phototropic face with diffusion layer is provided, the silicon substrate is p-type polycrystalline silicon silicon substrate, in silicon
The shady face deposition p-type zinc oxide of matrix, forms conducting medium layer；
S2, protective layer is prepared on the conducting medium layer, then prepare Al-BSF on the protection layer, the Al-BSF is passed through
The conducting medium layer and protective layer are worn, and is contacted simultaneously with silicon substrate, conducting medium layer；
S3, the shady face gate electrode line contacted with the Al-BSF is prepared on the protective layer of silicon substrate shady face, in silicon
The phototropic face gate electrode line contacted with diffusion layer is prepared on matrix phototropic face.
Method provided by the invention is prepared based on the silicon substrate for having diffusion layer on phototropic face.Wherein, on phototropic face
Silicon substrate with diffusion layer can use p-type polysilicon piece to be obtained after the making herbs into wool of routine, diffusion, etching, polishing.Above-mentioned system
Suede, diffusion, etching, polishing can use existing method, for above-mentioned making herbs into wool, diffusion, etching, the specific work of polishing in the present invention
Skill step is not particularly limited, and will not be repeated here.
According to the present invention, in above-mentioned steps S1, the method that p-type zinc oxide is deposited in the shady face of silicon substrate can be atom
Layer deposition (ALD) method.Adulterated by p-type and obtain p-type zinc oxide.
Specifically, in the step S1, the method for forming p-type zinc oxide is：By zinc source, nitrogen source, silicon source, oxygen source gasification simultaneously
Atomic deposition room is inputted, deposition processes are carried out under high pure nitrogen atmosphere；Zinc source, nitrogen source, silicon source, the material mol ratio of oxygen source are
1：(1-3)：(0.01-0.5)：(2-6).
Zinc source, nitrogen source, silicon source, oxygen source employed in the above method can use conventional various raw materials, specifically, this
In invention, the zinc source is zinc methide or diethyl zinc, and the nitrogen source is ammonia, and source of aluminium is trimethyl aluminium or triethyl group
Aluminium, the oxygen source are water.
The principle of present invention deposition p-type zinc oxide is to decompose and aoxidize to be formed on silicon silicon substrate surface by organic zinc source
Zinc oxide, and organic silicon source is decomposed and aoxidizes and formed aluminum oxide, in the aluminium atom that the nitrogen-atoms and organo-aluminium provided by ammonia provides
The zinc oxide of nitrogen aluminium permeation is obtained in the common zinc oxide for penetrating into silicon face, the doping zinc-oxide forms P-type semiconductor,
Its general process can schematically show as follows：
Si(s)+H2O(g)——Si-O-H(s)+H
Zn(CH3)2(g)+Si-O-H(s)——Si-O-Zn(CH3)(s)+CH4
2H2O(g)+Si-O-Zn(CH3)2(s)——Si-O-Zn-O-H(s)+2CH4
Al(CH3)3(g)+Si-O-H(s)——Si-O-Al(CH3)3(s)+CH4
2H2O(g)+Si-O-Al(CH3)2(s)——Si-O-Al(OH)2(s)+2CH4
NH3(g)——NH2(g)+NH(g)+3H(g)
In this process, the reaction of silicon and water, and the decomposable process of ammonia have atomic hydrogen generation, and the hydrogen-like is to P-type silicon
There is well passivated effect silicon substrate surface and inside, in addition, hydroxyl bond caused by water can also combine the suspension of silicon face
Key, so as to having certain passivation effect inside silicon silicon substrate surface and silicon silicon substrate, on the one hand reduce silicon silicon substrate
Defect concentration, the life-span of photo-generated carrier is added, on the other hand light path is added to a certain extent, increases silicon silicon substrate
Absorption to long wave, minority carrier life time also accordingly increase, therefore the short circuit current (Isc) of battery also obtains raising by a relatively large margin.
In addition, organo-aluminium decompose caused by nitrogen-atoms caused by aluminium atom and ammonolysis craft can partly substitute zinc oxide (or
Person is regarded as the zinc hydroxide combined with silicon silicon substrate surface by oxygen key, i.e. Si-O-Zn-O-H) in zinc atom and formed
Cavity type carrier, and its hole concentration is more than the hole concentration of P-type silicon silicon substrate, is measured using four-point probe device, its
Film resiativity is 0.01-0.1 Ω cm, so as to form PP+'s between P-type silicon silicon substrate and p-type zinc oxide conducting medium layer
Hetero-junctions, because the hole concentration in the p-type zinc oxide conducting medium layer diffuses into than the aluminium atom in aluminium paste forms aluminium in silicon
The hole concentration of back surface field is high, therefore the supplement photovoltaic voltage that the hetero-junctions of the PP+ obtains is tied to obtain than aluminium and silicon formation PP+
Supplement photovoltaic voltage will height, and the overall open-circuit voltage Voc of crystal silicon solar cell sheet be PN junction open pressure formed with PP+
Open pressure sum, therefore the open-circuit voltage of crystal silicon solar cell sheet of the present invention has greatly improved than conventional batteries.
In the present invention, to make atomic deposition reaction to be more smoothed out, and certain deposition velocity is made it have, preferably
In the case of, silicon silicon substrate can be heated to certain temperature, silicon substrate temperature is higher, and sedimentation rate is bigger, and the crystal grain of formation is also got over
Greatly, structure is also loose.But too high silicon substrate temperature (such as larger than more than 800 DEG C) can then cause P-type silicon within the long time
The defects of silicon substrate density increases considerably, and the serious minority carrier life time reduced in silicon silicon substrate, causes the decline of battery performance.
Silicon substrate temperature reduction, sedimentation rate then diminish, and the crystal grain of formation is also small, and the structure of p-type zinc oxide conducting medium layer is also becoming tight
It is close.In the present invention, under preferable case, silicon silicon substrate temperature is set as 600-800 DEG C, and the sedimentation rate of the film now obtained is
0.5-3.0nm/s。
Meanwhile according to the present invention, further to improve the performance of crystal silicon solar cell sheet, under preferable case, in silicon
The thickness of the p-type zinc oxide conducting medium layer of matrix shady face deposition also can control within the specific limits, and such as deposition is too thick, then needs
Increase the time of deposition, increase process costs, deposit too thin, then P-type silicon matrix and the PP+ that conducting medium layer is formed are heterogeneous
The effect of knot can reduce, and its electric conductivity can also decline, and cause the series resistance of cell piece to increase, to conveying photoproduction current-carrying
Son is unfavorable, and in the present invention, under preferable case, the deposit thickness of p-type zinc oxide conducting medium layer is 10-100nm, more preferably
20-50nm。
, generally, can also be in above-mentioned conducting medium layer to be protected to the p-type zinc oxide conducting medium layer of above-mentioned formation
Surface is using pecvd process plating silicon nitride film, the protective layer using the film layer as p-type zinc oxide conducting medium layer, so as to prevent
Conducting medium layer is scratched or destroyed by external force.Under preferable case, the thickness of above-mentioned protective layer is 50-300nm, more preferably 100-
300nm。
As existing, to improve the performance of crystal silicon solar cell sheet, generally, on the diffusion layer of silicon substrate phototropic face
Using the pecvd process of routine, plating silicon nitride film is as antireflective coating.The thickness of above-mentioned antireflective coating is usually 70-80nm.
As previously described, because the protective layer of silicon nitride material is non-conductive, in order in the back of the body of crystal silicon solar cell sheet
Smooth surface forms Al-BSF, and forms current channel, generally, using the protective layer and conducting medium layer in laser-ablated fraction region,
Form one fixed width and first groove at interval.First groove runs through the protective layer and conducting medium layer.
By printing aluminium paste on the protection layer, aluminium paste is at least filled first groove, aluminium is can obtain after sintered
Back surface field.
The arrangement form of above-mentioned first groove can use routine, for example, the protective layer is provided with multiple mutually flat
Capable first groove, the main gate line that the length direction of the first groove can be formed with the phototropic face of silicon substrate are perpendicular.
In the present invention, inventor has found, the width w of the first groove1And the centre distance c between two adjacent first grooves, to most
End form into the performance of crystal silicon solar cell sheet have an impact.According to the lifting of the present invention, for the benefit of minority carrier life time, and profit
In the formation of Al-BSF and the collection of photogenerated current, the width w of above-mentioned first groove1For 0.5-5mm, preferably 1-2mm.Phase
The distance between the center line of length direction of adjacent two the first grooves c is 5-10mm, preferably 6-8mm.
During construction, the edge of crystal silicon solar cell sheet is extended to prevent aluminium paste in the first groove from permeating or climbing, shadow
The electrical property of cell piece is rung, under preferable case, the end in the first groove length direction and the edge of silicon substrate have certain interval
Distance δ1, δ1Preferably 2-5mm.
In the present invention, when preparing Al-BSF, aluminium paste can be printed in protective layer, made in protective layer and the first groove
Aluminium paste is respectively provided with, or only fills aluminium paste in the first groove.As it was previously stated, the glass dust in the aluminium paste of protective layer is molten
Melt under state, may corrode and penetrate silicon nitride protective layer and have a negative impact.On the other hand, in the present invention, preferably only
Filling aluminium paste in one groove.Because the first groove size is smaller, for ease of construction, the specific of aluminium paste is filled only in the first groove
Method can be：The printing screen plate of an aluminium paste consistent with the first groove pattern is prepared, by printing screen plate and the first groove figure
Shape is corresponding, and aluminum back-surface-field conductive paste is printed into the first groove by above-mentioned printing screen plate.
After printing above-mentioned aluminium paste, it is baked to.Then shady face gate electrode line is prepared in protective layer.Shady face electrode
The preparation method of grid line can use existing various methods.For example, after the aluminium paste in printing and drying the first groove, with
On the perpendicular direction in first groove length direction, i.e., the phototropic face electrode main grid line identical that need to be formed with silicon substrate phototropic face
Direction, several continuous shady face silver paste bands are republished, the slurry tape number of printing, need to typically be formed with silicon substrate phototropic face
Phototropic face electrode main grid line number is identical, such as 2-4 bars, preferably 3, the width w of shady face silver paste band2For 2-5mm, to save
Silver paste, w2Preferably 2.5-3mm, end and the silicon substrate in shady face silver paste strip length direction similar with printing aluminium paste
Edge also needs to keep certain interval distance δ2, δ2It is set to 2-5mm.By follow-up sintering processes, above-mentioned shady face silver paste band is shape
Into shady face gate electrode line.
After shady face silver paste band is printed, drying, phototropic face silver paste band then is printed in the phototropic face of silicon substrate, after burning
Dry, sinter, you can obtain crystal silicon solar cell sheet in freezing of a furnace.The typography of phototropic face silver paste band, in sintering furnace
Sintering process, it is identical with the technique of current conventional crystal silicon solar cell sheet.For example, also wrapped before the step S3
Include, silicon nitride is plated on the diffusion layer of the silicon substrate, form antireflection layer, print silver paste on the antireflection layer, through burning
Orthogonal phototropic face electrode main grid line and phototropic face electrode pair grid line are obtained after knot.
The sintering method is：In sintering furnace, preheating temperature be 600-800 DEG C, peak temperature be 900-950 DEG C
Under the conditions of be sintered.
In the crystal silicon solar cell sheet being prepared using present invention process, the p-type that is obtained using ald
Zinc oxide conducting medium layer even compact, and there is higher hole density, therefore the p-type polycrystalline silicon than P-type silicon silicon substrate
Silicon substrate forms PP+ hetero-junctions with conducting medium layer, and the hetero-junctions has the function that to collect photo-generated carrier, therefore crystal simultaneously
The open-circuit voltage (Voc) of silicon solar cell is significantly improved, the series resistance (Rs) of crystal silicon solar cell sheet with
The back of the body passivation crystal silicon solar cell sheet (PERL) compare, also improve to a certain extent.Meanwhile the conducting medium layer is to silicon silicon
Matrix surface also has certain passivation effect, adds light path to a certain extent, increases suction of the silicon silicon substrate to long wave
To receive, minority carrier life time also accordingly increases, therefore the short circuit current (Isc) of crystal silicon solar cell sheet is also improved, also, because
The present invention only overleaf prints aluminium paste in laser grooving, therefore damage of the electrocondution slurry to conducting medium layer is also few, due to many
Factor influences, and crystal silicon solar cell sheet of the invention greatly improves the photoelectric transformation efficiency of battery.
The present invention is further detailed by the following examples.
Embodiment 1
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
1st, before plated film silicon chip preparation
The p-type polysilicon piece specification used for：156mm × 156mm, thickness is 200 μm, by silicon wafer wool making, diffusion, etching
Afterwards, silicon chip back side is processed by shot blasting, obtaining surface has the silicon substrate of diffusion layer.
2nd, the preparation of p-type zinc oxide conducting medium layer
Using the atomic layer deposition apparatus of Holland production Solay Tech InPassion ALD 3600, with zinc methide, ammonia
Zinc source, nitrogen source, silicon source and the oxygen source of gas, trimethyl aluminium, deionized water needed for as deposition, and zinc methide：Ammonia：Trimethyl
Aluminium：The material mol ratio of deionized water is 1：2：0.05：4.Silicon chip silicon substrate temperature is 650 DEG C, and sedimentation time is 20 seconds, deposition
Thickness is 32-35nm, is tested using RM-220 resistivity meters, and the resistivity of the film is 0.0464 Ω cm.
3rd, the preparation of silicon nitride anti-reflecting film and protective layer
Silicon nitride anti-reflecting film is plated using PECVD method in the phototropic face of silicon chip, phototropic face coating film thickness is 75-
80nm.The technique for plating silicon nitride anti-reflecting film is identical with the antireflective coating technique of conventional crystalline silicon solar cell.To light
After antireflective coating has been plated in face, the same method for using PECVD, silicon nitride film is plated as p-type zinc oxide conducting medium in shady face
The protective layer of layer, the thickness 145-155nm of silicon nitride protective layer.
4th, the preparation of the first groove
Use frequency to punch protective layer and p-type zinc oxide conducting medium layer for 200KHz lbgs, form the first groove.
The width w of first groove1For 2mm, adjacent first groove center distance c is 6mm, the end of the first groove and the edge of cell piece
Gap delta1For 3mm.
5th, back field aluminum paste is printed
The printing screen plate of an aluminium paste consistent with shady face the first groove pattern is prepared, by printing screen plate and the first groove
Figure is corresponding, aluminum back-surface-field conductive paste is printed into the first groove, slurry model uses Taiwan Shuo He scientific ＆ technical corporation 108C aluminium
Slurry.Dried using aluminium paste drying oven, drying oven design temperature is 150-300 DEG C, time 1-2min.
6th, printed back silver paste
It is continuous using 280 mesh, the screen painting three with a width of 2.5mm in the vertical direction with shady face aluminium paste band
Shady face silver paste band, obtain the width w of shady face silver paste band2For 2.5mm, the end in shady face silver paste strip length direction and silicon substrate
The distance δ at the edge of body2For 3mm.Shady face silver paste model uses the PV505 of Dupont companies of the U.S., drying.
7th, phototropic face silver paste and sintering are printed
The preparation technology of phototropic face gate electrode line is identical with the method for routine, that is, uses 400 mesh, line width as 60 μm of half tone
In the phototropic face printing phototropic face electrode silver plasm (using Dupont companies of U.S. 17F silver pastes) of battery, phototropic face electrode main grid line
It is set as three, printing weight in wet base is 100-120mg, then enters and sintering is dried in continuous tunnel furnace, and preheating temperature is 600-800 DEG C, peak
It is 920 DEG C to be worth temperature, and the whole time for crossing continuous tunnel furnace is 2 minutes or so, and peak value sintering time is 1 second or so.
Obtained crystal silicon solar cell sheet is designated as S1.Its structure referring to Fig. 1-Fig. 3, wherein, the phototropic face of silicon substrate 5 according to
Secondary to have diffusion layer 4, antireflection layer 3, diffusion layer 4 contacts with silicon substrate 5.Antireflection layer 3 runs through antireflection layer 3 provided with a plurality of
And the phototropic face electrode pair grid line 2 contacted with diffusion layer 4.A plurality of phototropic face electrode pair grid line 2 is parallel to each other.The table of antireflection layer 3
Face has three phototropic face electrode main grid lines 1 being parallel to each other.Three phototropic face electrode main grid lines 1 and phototropic face electrode pair grid line
2 is vertical and contact.
The shady face of silicon substrate 5 has conducting medium layer 6, protective layer 7 successively.Conducting medium layer 6 contacts with silicon substrate 5.Protect
Sheath 7 runs through protective layer 7 and conducting medium layer 6, and the aluminum strip being parallel to each other contacted with silicon substrate 5 provided with a plurality of, is formed
Al-BSF 8.The surface of protective layer 7 has three shady face gate electrode lines 9 being parallel to each other.Three shady face gate electrode lines 9 with to
Smooth surface electrode main grid line 1 is parallel.
Embodiment 2
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
The sedimentation time of p-type zinc oxide conducting medium layer in the step 2 of embodiment 1 is changed to 60 seconds, deposit thickness 90-
95nm, the resistivity for testing the conducting medium layer is 0.0453 Ω cm, and remaining technique and other steps are same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S2.
Embodiment 3
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
The sedimentation time of p-type zinc oxide conducting medium layer in the step 2 of embodiment 1 is changed to 7 seconds, deposit thickness 10-
12nm, the resistivity for testing the conducting medium layer is 0.0479 Ω cm, and remaining technique and other steps are same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S3.
Embodiment 4
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
Substance source in the step 2 of embodiment 1 is adjusted, makes zinc methide：Ammonia：Trimethyl aluminium：Deionized water
Material mol ratio is 1：3：0.05：4.The resistivity for testing the conducting medium layer is 0.0146 Ω cm, remaining technique and other steps
It is rapid same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S4.
Embodiment 5
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
Substance source in the step 2 of embodiment 1 is adjusted, makes zinc methide：Ammonia：Trimethyl aluminium：Deionized water
Material mol ratio is 1：2：0.5：4, the resistivity for testing the conducting medium layer is 0.0256 Ω cm, remaining technique and other steps
It is same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S5.
Embodiment 6
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
Substance source in the step 2 of embodiment 1 is adjusted, makes zinc methide：Ammonia：Trimethyl aluminium：Deionized water
Material mol ratio is 1: 2: 0.05: 6.The resistivity for testing the conducting medium layer is 0.0917 Ω cm, remaining technique and other steps
It is rapid same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S6.
Embodiment 7
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
Silicon substrate temperature in the step 2 of embodiment 1 is adjusted to 800 DEG C, sedimentation time is changed to 15 seconds, obtains p-type zinc oxide
The thickness of conducting medium layer is 30-35nm, and the resistivity for testing the conducting medium layer is 0.0547 Ω cm, remaining technique and other
Step is same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S7.
Embodiment 8
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
The thickness of shady face plating silicon nitride film protective layer in the step 3 of embodiment 1 is adjusted to 295-300nm.Remaining technique
And other steps are same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S8.
Embodiment 9
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
By the width w of the first groove in the step 4 of embodiment 11Be changed to 5mm, remaining technique and other steps with embodiment 1
It is identical.
Obtained crystal silicon solar cell sheet is designated as S9.
Embodiment 10
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
First groove adjacent slot centre distance c in the step 4 of embodiment 1 is adjusted to 10mm, remaining technique and other steps
It is same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S10.
Embodiment 11
The present embodiment is used to illustrate crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
The width w of shady face silver paste band will be printed in the step 6 of embodiment 125mm is adjusted to, remaining technique and other steps
It is same as Example 1.
Obtained crystal silicon solar cell sheet is designated as S11.
Comparative example 1
This comparative example is used for comparative illustration crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
1st, before plated film silicon chip preparation
The step and embodiment 1 are identical
2nd, the preparation of alumina medium layer
It is same as Example 1, it is same that atomic layer deposition is used as using Holland production Solay Tech InPassion ALD 3600
Product equipment, using the zinc source needed for trimethyl aluminium, deionized water as deposition and oxygen source.Now, silicon chip silicon substrate temperature is 250
DEG C, sedimentation time is 10 seconds, and the deposit thickness of obtained alumina passivation layer is 10-12nm, is then carried out under oxygen atmosphere
Annealing, annealing temperature are 550 DEG C, annealing time 10min；
3rd, the preparation of silicon nitride anti-reflecting film and protective layer
The step is same as Example 1.
4th, the preparation of the first groove
Frequency is used to punch protective layer and passivation layer for 200KHz lbgs, the width of the first groove is 50 μm, adjacent
First groove center distance is 1000 μm.
5th, shady face silver paste band is printed
Using 280 mesh silk-screen printing shady face silver paste bands (Dupont companies of U.S. PV505 silver pastes), using three lines, four sections of systems
(width 2.5mm), the printing weight in wet base of shady face silver paste is 35-50mg.Dried using drying oven, drying temperature 300-400
DEG C, time 1-2min.
6th, back field aluminum paste is printed
In the remaining all shady face parts of shady face silver paste, aluminum back-surface-field conductive paste (Taiwan Shuo He sections are printed using 250 mesh
Skill company 108C aluminium pastes), printing weight in wet base is 1.30-1.50g, is dried using drying oven, and drying temperature is 300-400 DEG C, the time
For 1-2min.
Obtained crystal silicon solar cell sheet is designated as DS1.
Comparative example 2
This comparative example is used for comparative illustration crystal silicon solar cell sheet disclosed by the invention and preparation method thereof.
1st, the preparation of the silicon chip before printing slurry
The p-type polysilicon piece specification used for：156mm × 156mm, thickness is 200 μm, by silicon wafer wool making, diffusion, etching
Afterwards, obtaining surface has the silicon substrate of diffusion layer.
2nd, shady face silver paste band is printed
Using 280 mesh silk-screen printing shady face silver paste bands (Dupont companies of U.S. PV505 silver pastes), using three lines, four sections of systems
(width 2.5mm), the printing weight in wet base of shady face silver paste is 35-50mg, is dried using drying oven, drying temperature 300-400
DEG C, time 1-2min.
3rd, back field aluminum paste is printed
In the remaining all shady face parts of shady face silver paste band, aluminum back-surface-field conductive paste (the large standing grain in Taiwan is printed using 250 mesh
Scientific ＆ technical corporation's 108C aluminium pastes), printing weight in wet base is 1.30-1.50g, is dried using aluminium paste drying oven, drying temperature 300-400
DEG C, time 1-2min.
4th, phototropic face silver paste band and sintering are printed
400 mesh, line width are used to print phototropic face electrode silver plasm band (using beautiful in the phototropic face of silicon substrate for 60 μm of half tone
Dupont companies of state 17F silver pastes), main gate line is set as three, and printing weight in wet base is 100-120mg, then enters in continuous tunnel furnace and dries
Sintering, preheating temperature are 600-800 DEG C, and peak temperature is 920 DEG C, and the whole time for crossing continuous tunnel furnace is 2 minutes or so, and peak value burns
It is 1 second or so to tie the time.
Obtained crystal silicon solar cell sheet is designated as DS2.
Performance test
Following performance test is carried out to above-mentioned the crystal silicon solar cell sheet S1-S11 and DS1-DS2 being prepared：
Surface appearance：Whether observation solar cell silver electrode surface has trachoma or pin hole etc., as being designated as OK without if, otherwise
It is designated as NG.
Short circuit current (Isc, unit A), open-circuit voltage (Uoc, unit V), peak power (Pmpp, unit W), fill factor, curve factor
(FF), electricity conversion (Eta, unit：%)：The above-mentioned unit for electrical property parameters of cell piece uses solar cell piece dedicated tester
Device, as single flash operation simulator is tested.Test condition is standard test condition (STC)：Light intensity：1000W/m2；Spectrum：
AM1.5；Temperature：25℃.Method of testing is carried out according to IEC904-1.
Obtained test result inserts table 1.
Table 1
| Sample | Surface appearance | Isc | Uoc | Pmpp | FF | Eta |
| S1 | OK | 8.7601 | 0.6364 | 4.4229 | 79.21 | 18.162 |
| S2 | OK | 8.6821 | 0.6353 | 4.3999 | 79.28 | 18.111 |
| S3 | OK | 8.7289 | 0.6349 | 4.4099 | 78.50 | 18.020 |
| S4 | OK | 8.7854 | 0.6367 | 4.4459 | 79.60 | 18.355 |
| S5 | OK | 8.6735 | 0.6356 | 4.4319 | 79.28 | 18.261 |
| S6 | OK | 8.7138 | 0.6342 | 4.3868 | 78.27 | 17.960 |
| S7 | OK | 8.7571 | 0.6370 | 4.4256 | 79.14 | 18.134 |
| S8 | OK | 8.7465 | 0.6338 | 4.3353 | 78.61 | 17.910 |
| S9 | OK | 8.7418 | 0.6348 | 4.3293 | 78.54 | 17.890 |
| S10 | OK | 8.7345 | 0.6346 | 4.3255 | 78.50 | 17.852 |
| S11 | OK | 8.7611 | 0.6375 | 4.4293 | 79.32 | 18.203 |
| DS1 | OK | 8.7354 | 0.6312 | 4.3113 | 78.47 | 17.745 |
| DS2 | OK | 8.5061 | 0.6259 | 4.2585 | 79.99 | 17.499 |
Embodiment S1-S11 test result compares the obtained crystalline silicon as can be seen that using the present invention from upper table 1
Solar battery sheet compared with conventional crystalline silicon solar cell DS1, the open-circuit voltage Voc of crystal silicon solar cell sheet and
Short circuit current Isc is significantly improved, and the photoelectric transformation efficiency of crystal silicon solar cell sheet obtains lifting by a relatively large margin,
Compared with the current back of the body passivation crystal silicon solar cell sheet DS1 that passivation layer is done using aluminum oxide, its open-circuit voltage Voc also has
Increase to a certain degree, and fill factor, curve factor FF increases, the photoelectric transformation efficiency of crystal silicon solar cell sheet have also obtained necessarily
Lifting.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (20)
1. a kind of crystal silicon solar cell sheet, it is characterised in that including silicon substrate, the shady face of the silicon substrate is sequentially provided with
Conducting medium layer, protective layer and shady face gate electrode line；The conducting medium layer contacts with the silicon substrate；The silicon substrate and
Al-BSF is additionally provided between shady face gate electrode line, the Al-BSF runs through the conducting medium layer and protective layer, and simultaneously
Contacted with silicon substrate, conducting medium layer and shady face gate electrode line；
The conducting medium layer material is p-type zinc oxide；
The silicon substrate is p-type polycrystalline silicon silicon substrate.
2. crystal silicon solar cell sheet according to claim 1, it is characterised in that the thickness of the conducting medium layer is
10-100nm。
3. crystal silicon solar cell sheet according to claim 1 or 2, it is characterised in that the conducting medium layer it is thin
Film resistivity is 0.01-0.1 Ω cm.
4. crystal silicon solar cell sheet according to claim 1, it is characterised in that it is recessed that the protective layer is provided with first
Groove, first groove are extended on silicon substrate through conducting medium layer；
The Al-BSF at least fills first groove.
5. crystal silicon solar cell sheet according to claim 4, it is characterised in that the Al-BSF is only located at described
In one groove.
6. the crystal silicon solar cell sheet according to claim 4 or 5, it is characterised in that the protective layer is provided with more
Individual first groove being parallel to each other；The width w of first groove1For 0.5-5mm, the end in the first groove length direction
With the distance δ at the silicon substrate edge1For 2-5mm, the distance between the center line of length direction of two neighboring first groove c
For 5-10mm.
7. crystal silicon solar cell sheet according to claim 6, it is characterised in that the shady face gate electrode line and institute
State the first texturearunaperpendicular；
The width w of the shady face gate electrode line2For 2-5mm, end and the silicon of the shady face gate electrode line length direction
The distance δ of matrix border2For 2-5mm.
8. according to the crystal silicon solar cell sheet described in any one in claim 1,2,4,5 or 7, it is characterised in that institute
It is silicon nitride to state protective layer material, and its thickness is 50-300nm.
9. crystal silicon solar cell sheet according to claim 1, it is characterised in that on the phototropic face of the silicon substrate according to
It is secondary that there is diffusion layer, antireflection layer and phototropic face gate electrode line；The antireflection layer material is silicon nitride, the antireflection layer
Thickness is 70-80nm；
The phototropic face gate electrode line includes orthogonal phototropic face electrode main grid line and phototropic face electrode pair grid line.
10. the preparation method of crystal silicon solar cell sheet as claimed in claim 1, it is characterised in that comprise the following steps：
S1, the silicon substrate on phototropic face with diffusion layer is provided, the silicon substrate is p-type polycrystalline silicon silicon substrate, in silicon substrate
Shady face deposition p-type zinc oxide, formed conducting medium layer；
S2, protective layer is prepared on the conducting medium layer, then prepare Al-BSF on the protection layer, the Al-BSF runs through institute
Conducting medium layer and protective layer are stated, and is contacted simultaneously with silicon substrate, conducting medium layer；
S3, the shady face gate electrode line contacted with the Al-BSF is prepared on the protective layer of silicon substrate shady face, in silicon substrate
The phototropic face gate electrode line contacted with diffusion layer is prepared on phototropic face.
11. preparation method according to claim 10, it is characterised in that in the step S1, form the side of p-type zinc oxide
Method is：Zinc source, nitrogen source, silicon source, oxygen source are gasified and input atomic deposition room, deposition processes are carried out under high pure nitrogen atmosphere；
Zinc source, nitrogen source, silicon source, the material mol ratio of oxygen source are 1：(1-3)：(0.01-0.5)：(2-6)；
The zinc source is zinc methide or diethyl zinc, and the nitrogen source is ammonia, and source of aluminium is trimethyl aluminium or triethyl aluminum,
The oxygen source is water.
12. preparation method according to claim 11, it is characterised in that the conduction is prepared on the shady face of silicon substrate
During dielectric layer, the temperature of the silicon substrate is 600-800 DEG C, and the sedimentation rate of conducting medium layer is 0.5-3.0nm/s.
13. according to the preparation method described in any one in claim 10-12, it is characterised in that in the shady face of silicon substrate
The thickness of the conducting medium layer of upper preparation is 10-100nm.
14. according to the preparation method described in any one in claim 10-12, it is characterised in that in the shady face of silicon substrate
The film resiativity of the conducting medium layer of upper preparation is 0.01-0.1 Ω cm.
15. preparation method according to claim 10, it is characterised in that in the step S2, after forming protective layer, use
Laser ablation protective layer and conducting medium layer surface, the first groove through the protective layer and conducting medium layer is formed, then
Aluminium paste is printed on the protection layer, aluminium paste is at least filled first groove, Al-BSF is obtained after sintered.
16. preparation method according to claim 15, it is characterised in that the aluminium paste is only filled with first groove
It is interior.
17. the preparation method according to claim 15 or 16, it is characterised in that by laser ablation, in the protective layer
It is upper to form multiple first grooves being parallel to each other；The width w of first groove1For 0.5-5mm, the first groove length side
To end and the silicon substrate edge distance δ1For 2-5mm, the center line of the length direction of two neighboring first groove it
Between distance c be 5-10mm.
18. preparation method according to claim 17, it is characterised in that in the step S3, edge and first groove
Perpendicular direction printing silver paste, obtains shady face gate electrode line after sintered；The width w of the shady face gate electrode line2For
2-5mm, the distance δ of the end of the shady face gate electrode line length direction and the silicon substrate edge2For 2-5mm.
19. preparation method according to claim 10, it is characterised in that also include before the step S3, in the silicon
Silicon nitride is plated on the diffusion layer of matrix, forms antireflection layer；
Silver paste is printed on the antireflection layer, orthogonal phototropic face electrode main grid line and phototropic face electricity are obtained after sintered
Extremely secondary grid line.
20. according to the preparation method described in any one in claim 15,16,18 or 19, it is characterised in that the sintering side
Method is：In sintering furnace, it is sintered under conditions of preheating temperature is 600-800 DEG C, peak temperature is 900-950 DEG C.
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| CN103367542A (en) * | 2013-07-02 | 2013-10-23 | 浙江正泰太阳能科技有限公司 | Crystalline silicon solar cell and preparation method thereof |
| CN103413838A (en) * | 2013-07-23 | 2013-11-27 | 新奥光伏能源有限公司 | Crystalline silicon solar cell and preparation method thereof |
| CN204230251U (en) * | 2014-11-27 | 2015-03-25 | 浙江昱辉阳光能源江苏有限公司 | A kind of heterojunction solar battery |
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| CN103367542A (en) * | 2013-07-02 | 2013-10-23 | 浙江正泰太阳能科技有限公司 | Crystalline silicon solar cell and preparation method thereof |
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