CN102064216A - Novel crystalline silicon solar cell and manufacturing method thereof - Google Patents
Novel crystalline silicon solar cell and manufacturing method thereof Download PDFInfo
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- CN102064216A CN102064216A CN2010105539782A CN201010553978A CN102064216A CN 102064216 A CN102064216 A CN 102064216A CN 2010105539782 A CN2010105539782 A CN 2010105539782A CN 201010553978 A CN201010553978 A CN 201010553978A CN 102064216 A CN102064216 A CN 102064216A
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Abstract
The invention discloses a novel crystalline silicon solar cell. The novel crystalline silicon solar cell comprises a crystalline silicon matrix, wherein the front surface of the crystalline silicon matrix has an emitter structure, and the back surface of the crystalline silicon matrix has a heterojunction structure; the heterojunction structure comprises an intrinsically hydrogenated amorphous silicon film, a hydrogenated amorphous silicon film, a transparent conductive oxide film and a metal conductive electrode in turn; the intrinsically hydrogenated amorphous silicon film covers the entire back surface of the crystalline silicon matrix; the hydrogenated amorphous silicon film is heavily doped by using a dopant which has the same conduction type as that of the matrix; and the metal conductive electrode passes through the transparent conductive oxide film and is in ohmic contact with a heavily doped layer. The invention also discloses a manufacturing method of the crystalline silicon solar cell. The crystalline silicon solar cell with the structure can reduce composite loss on the surface; meanwhile, the back surface of the solar cell forms a better light trap structure to improve open-circuit voltage of the solar cell, so that conversion efficiency of the solar cell is improved.
Description
Technical field
The invention belongs to the photovoltaic technology field, be specifically related to a kind of novel solar cell and manufacture craft thereof with high conversion efficiency.
Background technology
Photovoltaic technology is one and utilizes large-area p-n junction diode with the technology of conversion of solar energy for electric energy that this p-n junction diode is called solar cell.The semi-conducting material of making solar cell all has certain energy gap, when solar cell is subjected to solar radiation, the photon that energy surpasses energy gap produces electron hole pair in solar cell, p-n junction separates electron hole pair, the asymmetry of p-n junction has determined the flow direction of dissimilar photo-generated carriers, connects outwards power output by external circuit.This is similar with common electrochemical cell principle.Fig. 1 provides the basic structure of a p-type crystal-silicon solar cell.
The high conversion efficiency [W. Shockley and H.J. Queisser, J. Appl. Phys. 32,150 (1961)] about 30% of theory of the solar cell that forms by single p-n junction.In the solar cell of being made by various different materials, expensive compound semiconductor solar cell is mainly used in space and concentration photovoltaic system, and in addition, the single crystal silicon solar cell conversion efficiency is the highest.Monocrystalline silicon piece is mainly formed by the p type silicon ingot cutting of the boron-doping of adopting Czochralski (CZ) method to make, and the conversion efficiency of industrial mass-produced p type single crystal silicon solar cell is about 17%.In addition, the compound life-span that has shortened the minority carrier of p type uptake zone of the photo-generated carrier that defect and impurity causes, the matrix front and rear surfaces exists surface recombination, and n type heavily doped region exists auger recombination, more than these effects limit the raising of p type single crystal silicon solar cell conversion efficiency.
In these loss mechanism, surface recombination is a loss mechanism that mainly influences the solar cell conversion efficiency.The diffusion layer of the heavy doping low square resistance that adopts in order to obtain desirable contact resistance is as emitter, thereby forms high surface concentration, and the surface passivation of this battery is the comparison difficulty.The increase of the auger recombination that emitter region heavy doping causes can cause the short wave response variation equally.In order to address this problem, a kind of selective emitter solar battery structure produces, as shown in Figure 2, it is a kind of heavily expansion under metal grid lines, gently expand at the grid line zone line, be proved the blue spectrum response that can improve the front surface passivation and significantly improve the battery sheet, had a kind of battery structure of low contact resistance.The battery sheet of this structure can make conversion efficiency have a net increase of one percentage point usually.
But for a single crystal silicon solar cell at the direct plated metal in the matrix back side, the surface recombination of cell back face will reduce the density of the minority carrier of back of the body near surface, limit the raising of battery open circuit voltage.Between absorbed layer and metal level, insert the heavily doped back of the body field photo-generated carrier is caused potential barrier, stoped the diffusion of light induced electron, help to reduce recombination-rate surface to a certain extent, but for the silicon chip that the monoblock surface all is the Metal Contact district, the effect of this method is limited.
Summary of the invention
The object of the present invention is to provide a kind of novel crystal-silicon solar cell, the crystal-silicon solar cell with this structure can reduce the recombination losses of battery surface; Make the cell back face form light trapping structure preferably simultaneously, improved the open circuit voltage of solar cell, thereby improve its conversion efficiency.
The present invention also aims to provide the manufacture method of above-mentioned novel solar cell, can obtain the higher solar cell of conversion efficiency by this method.
First purpose of the present invention is achieved by the following technical solution: a kind of novel crystal silicon solar cell, comprise the crystalline silicon matrix, front surface at the crystalline silicon matrix has emitter structure, described emitter structure comprises diffusion layer, the zone of described diffusion layer under metal grid lines is heavily doped layer, zone between metal grid lines is a lightly-doped layer, the conductivity type opposite of wherein adulterant dopant and crystalline silicon matrix, described emitter structure also is included in antireflective coating and the front surface metallic conduction electrode on the diffusion layer, and described front surface metallic conduction electrode contacts with heavily doped region; Described crystalline silicon matrix has heterojunction structure overleaf, and described heterojunction structure comprises that successively one deck covers the intrinsic hydrogenated amorphous silicon film at the whole back side of crystalline silicon matrix; One deck adopts the dopant identical with the matrix conduction type to carry out heavily doped hydrogenated amorphous silicon film; Layer of transparent conductive oxide film and pass the transparent conductive oxide film and heavily doped layer forms the metallic conduction electrode of ohmic contact.
The thickness of intrinsic hydrogenated amorphous silicon film of the present invention and heavy doping hydrogenated amorphous silicon film is preferably 1 ~ 50nm.
Transparent conductive oxide film of the present invention is preferably indium oxide tin film or mixes the Zinc oxide film of aluminium.
Back metal conductive electrode of the present invention can cover the back side of whole solar cell, and the metallic conduction electrode at the back side of the whole solar cell of described covering can be aluminium film or aerdentalloy rete, and its thickness is 1 μ m ~ 20 μ m; Or described back metal conductive electrode can the cover part solar cell the back side, the metallic conduction electrode at the back side of described cover part solar cell can be silver grating line, alum gate line or aerdentalloy grid line, its width is 50 ~ 250 μ m, and thickness is 10 μ m ~ 50 μ m.
Antireflective coating of the present invention is preferably silicon nitride film, oxidation titanium film, silica silicon nitride composite membrane or silica titanium oxide composite membrane.
Crystalline silicon matrix of the present invention is p type or n type monocrystalline or polysilicon chip, and its resistivity is 0.1 ~ 10 Ω cm, and its thickness is 150 ~ 500 μ m.
Second purpose of the present invention is achieved by the following technical solution: the manufacture method of above-mentioned novel solar cell, contain following steps: at first form suede structure, form selective emitting electrode structure at crystalline silicon matrix front surface then on the two sides, front and back of crystalline silicon matrix; Then carry out chemical polishing at the crystalline silicon matrix back side, depositional coating successively, order is: intrinsic hydrogenated amorphous silicon film, heavy doping hydrogenated amorphous silicon film, transparent conductive oxide film and back metal conducting film, carry out the annealing process of battery sheet at last.
In above-mentioned manufacture method: the solution that adopts during chemical polishing is preferably KOH, NaOH, Tetramethylammonium hydroxide or ethylenediamine, wherein the weight percentage of KOH or NaOH is 10 ~ 40%, the weight percentage of Tetramethylammonium hydroxide or ethylenediamine is 10 ~ 30%, and the temperature during chemical polishing is 50 ~ 90 ℃.
Need Doping Phosphorus or boron during the deposition of heavily doped hydrogenated amorphous silicon film.Doping Phosphorus in the time of wherein will obtaining n type conductivity, doped with boron in the time of obtaining p type conductivity.
Preferred plasma reinforced chemical vapour deposition method or the heated filament sedimentation of adopting prepares intrinsic hydrogenated amorphous silicon film or heavy doping hydrogenated amorphous silicon film, and depositing temperature is 100 ~ 200 ℃; Adopt physical vaporous deposition to prepare the transparent conductive oxide film; Adopt the heavy vapour deposition process of silk screen printing or physics to prepare the back metal electrode; Annealing temperature when carrying out the annealing process of battery sheet is 200 ~ 300 ℃.
The invention has the beneficial effects as follows:
. the intrinsic hydrogenated amorphous silicon film has excellent surface passivation performance, the recombination-rate surface of minority carrier is dropped to minimum, so this technology can reduce the recombination losses of battery surface to a great extent;
Description of drawings
Fig. 1 is by the sectional view of the single p-n junction solar cell of a kind of common process preparation on p type crystalline silicon matrix; Among Fig. 1: 1, contact grid line; 2, passivation/antireflection layer; 3, n
++Layer (emitter); 4, matrix; 5, back side contact;
Fig. 2 is the sectional view of a kind of selective emitter solar battery of being made by common process on p type crystalline silicon matrix; 1, selective emitter; 2, matrix; 3, BSF/ back side contact; 4, light diffusion region (n
+); 5, heavy diffusion region (n
++);
Fig. 3 is the sectional view of the back of the body contact of making on p type crystalline silicon matrix among the embodiment 1; 1, selective emitter; 2, matrix; 3, intrinsic a-Si:H film; 4, doping a-Si:H film; 5, TCO film; 6, metallic conduction electrode; 7, light diffusion region (n
+); 8, heavy diffusion region (n
++);
Fig. 4 is the sectional view of the back of the body contact of making on p type crystalline silicon matrix among the embodiment 2.1, selective emitter; 2, matrix; 3, intrinsic a-Si:H film; 4, doping a-Si:H film (P); 5, TCO film; 6, metallic conduction contact grid line; 7, light diffusion region (n
+); 8, heavy diffusion region (n
++).
Embodiment
This disclosure of the Invention be the design that crystal-silicon solar cell obtains maximum conversion efficiency of solar cell.The matrix of solar cell can adopt lightly doped monocrystalline silicon piece or the polysilicon chip of resistivity at 0.1 ~ 10 Ω cm.The front surface of matrix has selective emitting electrode structure, and this structure is heavily diffusion under metal grid lines, the light diffusion in the zone between grid line, thus obtain low contact resistance.Light diffusion region and heavy diffusion region have formed the conductivity opposite with matrix (for example: matrix is the p type, and corresponding heavy diffusion region and light diffusion region are the n types, and vice versa) when diffusion.Deposit one deck antireflective coating (as: silicon nitride film or silicon dioxide film, the perhaps stack membrane of silica and silicon nitride) on the front surface, wherein had only heavy diffusion region and Metal Contact.Deposit one deck intrinsic (undoping fully) amorphous silicon hydride (a-Si:H) film at first at the back side of solar cell matrix (being preferably in whole back of the body surface), deposit one deck heavy doping amorphous silicon hydride (a-Si:H) film identical again with matrix conductivity.Deposition layer of transparent conductive oxide (TCO) film on whole heavy doping a-Si:H film, next, preparation one deck back metal conducting film (as: Al film or Al/Ag alloy-layer) forms ohmic contact with the TCO film on whole tco layer.
The manufacture method of this solar cell is as follows: (1) adopts the wet chemical etch method to form suede structure on the two sides of matrix; (2) clean and process for etching after, carry out the diffusion technology with the alloy of silicon substrate conductivity type opposite, different doping contents formation selective emitter when utilizing diffusion; Afterwards at front surface deposition antireflective film, at the contact grid line of front surface preparation as conductive electrode; (3) remove the reverse diffusion layer that forms in the step 1 with chemical polishing and form the smooth back side simultaneously, can stop the conducting at the front doped region and the back side; (4) order at matrix back side depositional coating successively is: intrinsic a-Si:H film, heavy doping a-Si:H film, TCO film and back metal conducting film; (5) annealing process of solar cell.Its concrete battery means as shown in Figure 3.Intrinsic a-Si:H layer and heavy doping a-Si:H layer can pass through plasma reinforced chemical vapour deposition (PECVD) or the preparation of heated filament sedimentation.The solution that is used for chemical polishing (for example: the aqueous solution) comprising: KOH, NaOH, Tetramethylammonium hydroxide (TMAH) and ethylenediamine (H
2NCH
2CH
2NH
2).The optium concentration of solution is 10% ~ 40%.The temperature of solution need remain on 50 ℃ ~ 90 ℃ during chemical polishing.The best proportioning of above solution is: 10% ~ 40%NaOH or 10% ~ 40%KOH or 10% ~ 30% Tetramethylammonium hydroxide or 10% ~ 30% ethylenediamine solution.Adopt identical deposition process when preparing intrinsic a-Si:H film, want Doping Phosphorus (obtaining n type conductivity) or boron (obtaining p type conductivity) when the difference of the two is deposition of heavily doped a-Si:H film with heavy doping a-Si:H film.The optimum thickness of intrinsic a-Si:H film and heavy doping a-Si:H film is 1 ~ 50nm, and depositing temperature is normally at 100 ~ 200 ℃.The TCO film is that the thickness with physical vapor deposition (PVD) method preparation is the indium oxide tin film (ITO) of 10 ~ 200nm or the Zinc oxide film (Al:ZnO) of mixing aluminium, and the back metal conducting film is that the thickness by silk screen printing or physical vapour deposition (PVD) preparation is 1 ~ 20 micron aluminium film or aluminium/silver alloy film.In this embodiment, the back side of whole solar cell has all formed the back metal contact.In order to reduce the contact resistance of front surface and back metal conducting film, can finish in the entire cell preparation and carry out annealing in process.Best annealing process temperature is 200 ℃ ~ 300 ℃.
Fig. 4 is the solar cell junction composition of present embodiment.It is a kind of that present embodiment provides can be the photovoltaic cell of electric energy with conversion of solar energy, and its structure is as follows: a kind of crystalline silicon matrix of conduction type, matrix can be monocrystalline silicon piece or polysilicon chip.The front surface of matrix has emitter structure, and this structure is heavily to expand under metal grid lines, and the zone between grid line is light expands the dopant wherein and the conductivity type opposite of matrix; This structure is included in an one deck antireflective coating and the cover front surface metallic conduction electrode on the diffusion layer; The back side at matrix has heterojunction structure, and this structure comprises: one deck covers intrinsic amorphous silicon hydride (a-Si:H) film at the whole back side of matrix; One deck adopts the dopant identical with the matrix conduction type to carry out heavily doped amorphous silicon hydride (a-Si:H) film; Layer of transparent conducting film and pass conducting film and heavily doped layer forms the metallic conduction electrode of ohmic contact.
The manufacture method of above-mentioned solar cell comprises: (1) adopts the wet chemical etch method to form suede structure on the two sides of matrix; (2) clean and process for etching after, carry out the diffusion technology with the alloy of silicon substrate conductivity type opposite, different doping contents formation selective emitter when utilizing diffusion; Afterwards at front surface deposition antireflective film, at the contact grid line of front surface preparation as conductive electrode; (3) remove the reverse diffusion layer that forms in the step 1 with chemical polishing and form the smooth back side simultaneously, can stop the conducting at the front doped region and the back side; (4) order at matrix back side depositional coating successively is: intrinsic a-Si:H film, heavy doping a-Si:H film, TCO film and back metal conduction grid line; (5) annealing process of solar cell.Intrinsic a-Si:H layer and heavy doping a-Si:H layer can pass through plasma reinforced chemical vapour deposition (PECVD) or the preparation of heated filament sedimentation.The solution that is used for chemical polishing (for example: the aqueous solution) comprising: KOH, NaOH, Tetramethylammonium hydroxide (TMAH) and ethylenediamine (H
2NCH
2CH
2NH
2).The optium concentration of solution is 10% ~ 40%.The temperature of solution need remain on 50 ℃ ~ 90 ℃ during chemical polishing.The best proportioning of above solution is: 10% ~ 40%NaOH or 10% ~ 40%KOH or 10% ~ 30% Tetramethylammonium hydroxide or 10% ~ 30% ethylenediamine solution.Adopt identical deposition process when preparing intrinsic a-Si:H film, want Doping Phosphorus (obtaining n type conductivity) or boron (obtaining p type conductivity) when the difference of the two is deposition of heavily doped a-Si:H film with heavy doping a-Si:H film.The optimum thickness of intrinsic a-Si:H film and heavy doping a-Si:H film is 1 ~ 50nm, and depositing temperature is normally at 100 ~ 200 ℃.The TCO film is that the thickness for preparing with the physical vapor deposition (PVD) method is the indium oxide tin film (ITO) of 10 ~ 200nm or the Zinc oxide film (Al:ZnO) of mixing aluminium.Back metal conduction grid line is that the width for preparing by silk screen printing or physical vapour deposition (PVD) is 50 ~ 250 microns, and thickness is 10 ~ 50 microns aluminium film or aluminium/silver alloy grid line.In this embodiment, as shown in Figure 4, this type of solar cell is except changing the back metal conducting film at the metallic conduction electrode (as: grid or grid line) that is complementary with surperficial grid line, and its structure is identical with the solar battery structure of execution mode one.Compared with the solar cell in the execution mode one, thereby the solar cell in the execution mode two can be captured the sunlight that enters from the back side at the cell back face and obtained high conversion rate.In order to reduce the contact resistance of front surface and back metal conduction grid line, can finish in the entire cell preparation and carry out annealing in process.Best annealing process temperature is 200 ℃ ~ 300 ℃.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included in protection scope of the present invention.
Claims (10)
1. novel crystal silicon solar cell, it is characterized in that: comprise the crystalline silicon matrix, front surface at the crystalline silicon matrix has emitter structure, described emitter structure comprises diffusion layer, the zone of described diffusion layer under metal grid lines is heavily doped layer, zone between metal grid lines is a lightly-doped layer, the conductivity type opposite of wherein adulterant dopant and crystalline silicon matrix, described emitter structure also is included in antireflective coating and the front surface metallic conduction electrode on the diffusion layer, and described front surface metallic conduction electrode contacts with heavily doped region; Described crystalline silicon matrix has heterojunction structure overleaf, and described heterojunction structure comprises that successively one deck covers the intrinsic hydrogenated amorphous silicon film at the whole back side of crystalline silicon matrix; One deck adopts the dopant identical with the matrix conduction type to carry out heavily doped hydrogenated amorphous silicon film; Layer of transparent conductive oxide film and form the metallic conduction electrode of ohmic contact with the transparent conductive oxide film.
2. novel crystal silicon solar cell according to claim 1 is characterized in that: the thickness of described intrinsic hydrogenated amorphous silicon film and heavy doping hydrogenated amorphous silicon film is 1 ~ 50nm.
3. novel crystal silicon solar cell according to claim 1 is characterized in that: described transparent conductive oxide film is indium oxide tin film or the Zinc oxide film of mixing aluminium.
4. novel crystal silicon solar cell according to claim 1, it is characterized in that: described back metal conductive electrode covers the back side of whole solar cell, the metallic conduction electrode at the back side of the whole solar cell of described covering is aluminium film or aerdentalloy rete, and its thickness is 1 μ m ~ 20 μ m; Or the back side of described back metal conductive electrode cover part solar cell, the metallic conduction electrode at the back side of described cover part solar cell is silver grating line, alum gate line or aerdentalloy grid line, and its width is 50 ~ 250 μ m, and thickness is 10 μ m ~ 50 μ m.
5. novel crystal silicon solar cell according to claim 1 is characterized in that: described antireflective coating is silicon nitride film, oxidation titanium film, silica silicon nitride composite membrane or silica titanium oxide composite membrane.
6. novel crystal silicon solar cell according to claim 1 is characterized in that: described crystalline silicon matrix is p type or n type monocrystalline or polysilicon chip, and its resistivity is 0.1 ~ 10 Ω cm, and its thickness is 150 ~ 500 μ m.
7. the manufacture method of each described novel crystal silicon solar cell of claim 1-6 is characterized in that containing following steps: at first form suede structure on the two sides, front and back of crystalline silicon matrix; Form selective emitting electrode structure at crystalline silicon matrix front surface then; Then carry out chemical polishing at the crystalline silicon matrix back side, depositional coating successively, order is: intrinsic hydrogenated amorphous silicon film, heavy doping hydrogenated amorphous silicon film, transparent conductive oxide film and back metal conductive electrode, carry out the annealing process of battery sheet at last.
8. the manufacture method of novel crystal silicon solar cell according to claim 7, it is characterized in that: the solution that adopts during chemical polishing is KOH, NaOH, Tetramethylammonium hydroxide or ethylenediamine, wherein the weight percentage of KOH or NaOH is 10 ~ 40%, the weight percentage of Tetramethylammonium hydroxide or ethylenediamine is 10 ~ 30%, and the temperature during chemical polishing is 50 ~ 90 ℃.
9. the manufacture method of novel crystal silicon solar cell according to claim 7 is characterized in that: need Doping Phosphorus or boron during the deposition of heavily doped hydrogenated amorphous silicon film.
10. the manufacture method of novel crystal silicon solar cell according to claim 7, it is characterized in that: adopt plasma reinforced chemical vapour deposition method or heated filament sedimentation to prepare intrinsic hydrogenated amorphous silicon film or heavy doping hydrogenated amorphous silicon film, depositing temperature is 100 ~ 200 ℃; Adopt physical vaporous deposition to prepare the transparent conductive oxide film; Adopt the heavy vapour deposition process of silk screen printing or physics to prepare the back metal electrode; Annealing temperature when carrying out the annealing process of battery sheet is 200 ~ 300 ℃.
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| CN102290449A (en) * | 2011-07-28 | 2011-12-21 | 河北工业大学 | Anti-reflection film system of polycrystalline silicon solar cell and preparation method for anti-reflection film system |
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