CN103311367A - Crystalline silicon solar cell manufacturing method - Google Patents
Crystalline silicon solar cell manufacturing method Download PDFInfo
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- CN103311367A CN103311367A CN2013102146268A CN201310214626A CN103311367A CN 103311367 A CN103311367 A CN 103311367A CN 2013102146268 A CN2013102146268 A CN 2013102146268A CN 201310214626 A CN201310214626 A CN 201310214626A CN 103311367 A CN103311367 A CN 103311367A
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Abstract
The invention discloses a crystalline silicon solar cell manufacturing method, which comprises the following steps of forming a sueding plane on the front surface of a P-type silicon wafer; forming a P-N junction on the front surface of the P-type silicon wafer; forming a metal layer on the P-N junction; forming a reflection reducing layer on the metal layer; forming a back electrode/aluminum back surface field on the back surface of the P-type silicon wafer; and forming a positive electrode on the front surface of the P-type silicon wafer. The method is characterized in that the barrier height formed between the metal layer and an N-type layer is smaller than the barrier height formed between the positive electrode and the N-type layer. Correspondingly, the invention also provides a crystalline silicon solar cell which is produced by the manufacturing method. By using the method, the contact problem between the n layer and a metal electrode, caused by a low-dosage concentration emitting electrode, is solved; the popularization of a high sheet resistance technology is facilitated; and a serial resistor of the crystalline silicon solar cell can be reduced, so that the conversion efficiency of the solar cell is improved.
Description
Technical field
The present invention relates to technical field of solar batteries, relate in particular to a kind of preparation method of crystal silicon solar energy battery.
Background technology
When metal contacts with semiconductor, will produce a potential barrier, barrier height Ф at the contact interface place
BRelevant with work function and the semi-conductive affine energy of metal.This potential barrier will hinder charge carrier to one of them direction transmission, and namely it has rectification characteristic.Eliminate the impact of this potential barrier, can carry out heavy doping to semi-conducting material.Barrier region between metal and the heavily-doped semiconductor can be very narrow, and charge carrier can unhinderedly pass potential barrier by tunneling effect.
Therefore, former crystal silicon solar energy battery generally all adopts the n layer emitter (that is: low square resistance) of high-dopant concentration, makes between n layer and metal (Ag) electrode to have lower contact resistance.But it is compound that the n layer emitter of employing high-dopant concentration will increase surperficial charge carrier, reduce the performance of solar cell.Have bibliographical information to point out, when the sheet resistance of emitter was 45 Ω/sq, surperficial charge carrier recombination rate reached 180,000cm/s; And the sheet resistance of emitter is when being 100 Ω/sq, and surperficial charge carrier recombination rate only has 60,000cm/s(Progressin Photovoltaic, 2006, vol.14, pp.135-144).
Present stage, photovoltaic industry generally adopted the n layer emitter (that is: high square resistance technology) of low doping concentration to improve the performance of crystal silicon solar energy battery.Because it is compound that the n layer emitter of low doping concentration can reduce surperficial charge carrier, make the sunlight that battery can better the radiothermy zone, and then improve short-circuit current density Jsc.But in the situation of the n layer emitter that adopts low doping concentration, can not form very narrow barrier region between argent electrode and n layer emitter, charge carrier can't tunnelling be crossed potential barrier, can cause having at the interface larger contact resistance, so the n layer emitter of low doping concentration and the contact resistance between metal electrode become the restraining factors of further raising battery efficiency.
Summary of the invention
The present invention proposes a kind of method that electrode and low doping concentration n layer emitter Contact resistance before the metal improve battery performance that reduces.Compare the larger barrier height Ф that can form when Ag contacts with N-shaped silicon
B, magnesium metal (Mg), titanium (Ti), hafnium (Hf), caesium (Cs) etc. have less barrier height Ф when contacting with N-shaped silicon
BThis layer metal has lower barrier height when contacting with the n layer, can reduce contact resistance, and this conclusion is proved (IEEE Transactions on Electron Devices, 1984, vol.31, pp.637-647) in pertinent literature; Simultaneously contacting between electrode and the described metal level then belongs to ohmic contact fully before the metal.Therefore, the present invention inserts the metal that one deck has above-mentioned characteristic between n layer emitter and argent, with the contact resistance between electrode and the n layer emitter before the reduction metal, and then the series resistance of reduction crystal silicon solar energy battery, with the raising solar cell properties, and can promote that low-doped n layer emitter technology further promoted.
According to an aspect of the present invention, provide a kind of preparation method of crystal silicon solar energy battery, described method comprises the steps:
A) form matte in the front of P type silicon chip;
B) form the P-N knot at described P type front side of silicon wafer;
C) tie the formation metal level at described P-N;
D) form anti-reflection layer at described metal level;
E) form back electrode/aluminium back surface field at described P type silicon chip back side;
F) form positive electrode at described P type front side of silicon wafer;
It is characterized in that, the barrier height that forms between described metal level and the N-type layer is less than the barrier height that forms between described positive electrode and the described N-type layer.
According to a preferred embodiment of the present invention, in described step c), adopt thermal evaporation, magnetron sputtering or electro-plating method to form described metal level at described P type front side of silicon wafer.
According to another preferred embodiment of the present invention, the metal in the described metal level comprises: magnesium, titanium, hafnium or caesium.
According to another aspect of the present invention, provide a kind of crystal silicon solar energy battery, described crystal silicon solar energy battery comprises from the bottom to top successively: back electrode/aluminium back surface field, P type silicon chip, P-N knot, metal level, anti-reflection layer and front electrode; It is characterized in that,
The barrier height that forms between described metal level and the N-type layer is less than the barrier height that forms between described positive electrode and the described N-type layer.
According to a further aspect of the invention, provide a kind of preparation method of crystal silicon solar energy battery, described method comprises the steps:
A) form matte in the front of N-type silicon chip;
B) form the N-P knot at described N-type front side of silicon wafer;
C) tie the formation metal level at described N-P;
D) form anti-reflection layer at described metal level;
E) form back electrode/aluminium back surface field at described N-type silicon chip back side;
F) form positive electrode at described N-type front side of silicon wafer;
It is characterized in that, the barrier height that forms between described metal level and the P type layer is less than the barrier height that forms between described positive electrode and the described P type layer.
According to a further aspect of the invention, provide a kind of crystal silicon solar energy battery, described crystal silicon solar energy battery comprises from the bottom to top successively: back electrode/aluminium back surface field, N-type silicon chip, N-P knot, metal level, anti-reflection layer and front electrode; It is characterized in that,
The barrier height that forms between described metal level and the P type layer is less than the barrier height that forms between described positive electrode and the described P type layer.
Adopt method of the present invention, can effectively solve n layer that the low doping concentration emitter causes and the contact problems between metal electrode, be conducive to wideling popularize of high square resistance technology; Can reduce the series resistance of crystal silicon solar energy battery, and then improve battery conversion efficiency; And simple and easy to do in actual preparation technology, carry out well compatibility with the product Wiring technology, be convenient to industrially promote.
Description of drawings
By reading the detailed description that non-limiting example is done of doing with reference to the following drawings, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 shows the schematic flow sheet according to a kind of embodiment of the preparation method of crystal silicon solar energy battery of the present invention;
Fig. 2 shows a kind of structural representation of embodiment of the crystal silicon solar energy battery of preparation method provided by the invention preparation.
Same or analogous Reference numeral represents same or analogous parts in the accompanying drawing.
Embodiment
Disclosing hereinafter provides many different embodiment or example to be used for realizing different structure of the present invention.Of the present invention open in order to simplify, hereinafter parts and the setting of specific examples are described.In addition, the present invention can be in different examples repeat reference numerals and/or letter.This repetition is in order to simplify and purpose clearly, itself not indicate the relation between the various embodiment that discuss of institute and/or the setting.Should be noted that illustrated parts are not necessarily drawn in proportion in the accompanying drawings.The present invention has omitted description to known assemblies and treatment technology and technique to avoid unnecessarily limiting the present invention.
With reference to figure 1, Fig. 1 is the schematic flow sheet of a kind of preparation method of crystal silicon solar energy battery among the present invention.
Step S101 forms matte in the front of P type silicon chip 100.Described P type silicon chip 100 is monocrystalline silicon, polysilicon or quasi-monocrystalline silicon.Form matte on the surface of P type silicon chip 100, light trapping effect that can Effective Raise P type silicon chip 100.Usually can adopt corrosive solution that the surface of P type silicon chip 100 is corroded, to form matte.Generally speaking, after the alkaline solution processing, can obtain the pyramid shape matte on the surface of P type silicon chip 100; After the acid solution processing, can obtain on the surface of P type silicon chip 100 worm channel shape matte.Except with the corrosive solution corrosion making herbs into wool, can also adopt dry method making herbs into wool, such as the reactive ion etching method etc.
Step S102 is at the described P type silicon chip 100 positive P-N knots 200 that form.Front at described P type silicon chip 100 forms the N-type layer, can adopt the phosphorus source of phosphorus element-containing to carry out the thermal diffusion of phosphorus in P type silicon chip 100 fronts, forms the N-type layer.Can also then process by rapid thermal annealing (Rapid Thermal Annealing) first in the phosphorous doped source of the front of P type silicon chip 100 spraying, finish the front phosphorus diffusion of silicon chip, namely form P-N knot 200.Then remove the phosphorosilicate glass in P type silicon chip 100 fronts.
Except adopting diffusion method to form P-N knot 200, can also adopt the method for Implantation to form P-N knot 200.The method of the formation P-N knot 200 that this area is commonly used is not particularly limited at this all applicable to the present invention.
Step S103 forms metal level 300 at described P-N knot 200.The barrier height that forms between the N-type layer in described metal level 300 and the P-N knot 200 is tied the barrier height that forms between the N-type layer in 200 less than the positive electrode 610 of follow-up formation and described P-N.Preferably, described metal level 300 can adopt thermal evaporation, magnetron sputtering or electro-plating method preparation to form.
Optionally, the material of described metal level 300 includes but not limited to magnesium metal (Mg), titanium (Ti), hafnium (Hf), caesium (Cs) etc., when above-mentioned metal contacts with the N-type layer, and the barrier height that the barrier height of generation produces when contacting with silver less than the N-type layer.Because with respect to metal Ti, Hf and Cs, metal M g is cheap, and preparation is simple, and therefore preferred Mg is as the material of metal level 300.
Optionally, the thickness range of described metal level 300 is 2nm～20nm, and is preferred, for example: 2nm, 14nm or 20nm.
Step S104 forms anti-reflection layer 400 at described metal level 300.Deposition anti-reflection layer 400 can adopt various conventional method well known to those skilled in the art, and the material of anti-reflection layer 400 can adopt various suitable materials, includes but not limited to silicon nitride (SiNx) material of commonly using.
In a preferred embodiment, P type silicon chip 100 is placed the tubular type PECVD stove of hydrogen atmosphere, 400 ℃～800 ℃ of temperature, preliminary treatment 5min～30min; Then boiler tube is evacuated to 0Pa～50Pa, removes residual gas; Constant pressure 0.5min～2min is filled with silane and ammonia, deposited silicon nitride anti-reflection layer 400.
Optionally, the thickness range of described anti-reflection layer 400 is 50nm～80nm, and is preferred, for example: 50nm, 65nm or 80nm.
Step S105 forms back electrode 620/ aluminium back surface field 500 at described P type silicon chip 100 back sides.Aluminium back surface field 500 has the function of passivation and transoid, can further reduce charge carrier compound, improves minority carrier life time, improves battery efficiency.Method by silk screen printing is at back up one deck aluminium paste of P type silicon chip 100, and then sintering can form aluminium back surface field 500.
Step S106 is at the described P type silicon chip 100 positive positive electrodes 610 that form.Optionally, above-mentioned back electrode 620 and/or positive electrode 610 can adopt printing or the mode of electroplating prepares.
With reference to figure 2, Fig. 2 shows a kind of structural representation of embodiment of the crystal silicon solar energy battery of preparation method provided by the invention preparation.As can be seen from Figure 2, described crystal silicon solar energy battery comprises from the bottom to top successively: back electrode 620/ aluminium back surface field 500, P type silicon chip 100, P-N knot 200, metal level 300, anti-reflection layer 400 and front electrode 610.
Wherein, P type silicon chip 100 is a kind of in monocrystalline silicon, polysilicon or the quasi-monocrystalline silicon.Surface at P type silicon chip 100 is formed with matte, the light trapping effect of suede structure Effective Raise P type silicon chip 100.
P type silicon chip 100 form P-N knot 200, P-N knot 200 can diffusion method or ion implantation form, the present invention is not specifically limited.
Optionally, the material of described metal level 300 includes but not limited to magnesium metal (Mg), titanium (Ti), hafnium (Hf), caesium (Cs) etc., when above-mentioned metal contacts with the N-type layer, and the barrier height that the barrier height of generation produces when contacting with silver less than the N-type layer.Because with respect to metal Ti, Hf and Cs, metal M g is cheap, and preparation is simple, and therefore preferred Mg is as the material of metal level 300.
Optionally, the thickness range of described metal level 300 is 2nm～20nm, and is preferred, for example: 2nm, 14nm or 20nm.
Aluminium back surface field 500 has the function of passivation and transoid, can further reduce charge carrier compound, improves minority carrier life time, improves battery efficiency.Aluminium back surface field 500 is formed by aluminium paste.Back electrode 620 can adopt the mode of printed silver slurry or electro-coppering to prepare.The preferred silvery electrode that adopts.
The present invention also provides a kind of crystal silicon solar energy battery that is prepared at the N-type silicon chip, and the preparation method is as follows: the front at the N-type silicon chip forms matte; Form the N-P knot at described N-type front side of silicon wafer; Tie the formation metal level at described N-P; Form anti-reflection layer at described metal level; Form back electrode/aluminium back surface field at described N-type silicon chip back side; Form positive electrode at described N-type front side of silicon wafer; The barrier height that forms between described metal level and the P type layer is less than the barrier height that forms between described positive electrode and the described P type layer.
Preferably, adopt thermal evaporation, magnetron sputtering or electro-plating method to form described metal level at described N-type front side of silicon wafer.Optionally, the metal in the described metal level comprises: magnesium, titanium, hafnium or caesium.Because the price comparison of titanium, hafnium or caesium is expensive, therefore the preferred magnesium metal that adopts forms metal level now.
Optionally, the thickness range of described metal level is 2nm～20nm, for example: 2nm, 11nm or 20nm.
In addition, corresponding the present invention also provides a kind of crystal silicon solar energy battery that adopts the said method preparation, and described crystal silicon solar energy battery comprises from the bottom to top successively: back electrode/aluminium back surface field, N-type silicon chip, N-P knot, metal level, anti-reflection layer and front electrode; The barrier height that forms between described metal level and the P type layer is less than the barrier height that forms between described positive electrode and the described P type layer.
It should be noted that; because above-mentioned crystal silicon solar energy battery for preparing take P type silicon chip as substrate and preparation method thereof is described in detail; and crystal silicon solar energy battery and preparation method thereof of preparation is with similar during as substrate take P type silicon chip take the N-type silicon chip as substrate; those skilled in the art are appreciated that the technical scheme that the present invention needs protection by the explanation of reading above-mentioned appropriate section; therefore just done concise and to the point description at this, corresponding technical characterictic has been repeated no more.
Adopt method of the present invention, can effectively solve n layer that the low doping concentration emitter causes and the contact problems between metal electrode, improve the photoelectric conversion efficiency of solar cell.
Although describe in detail about example embodiment and advantage thereof, be to be understood that in the situation of the protection range that does not break away from the restriction of spirit of the present invention and claims, can carry out various variations, substitutions and modifications to these embodiment.For other examples, when those of ordinary skill in the art should easily understand within keeping protection range of the present invention, the order of processing step can change.
Claims (13)
1. the preparation method of a crystal silicon solar energy battery, described method comprises the steps:
A) form matte in the front of P type silicon chip;
B) form the P-N knot at described P type front side of silicon wafer;
C) tie the formation metal level at described P-N;
D) form anti-reflection layer at described metal level;
E) form back electrode/aluminium back surface field at described P type silicon chip back side;
F) form positive electrode at described P type front side of silicon wafer;
It is characterized in that, the barrier height that forms between described metal level and the N-type layer is less than the barrier height that forms between described positive electrode and the described N-type layer.
2. preparation method according to claim 1 is characterized in that, in described step c), adopts thermal evaporation, magnetron sputtering or electro-plating method to form described metal level at described P type front side of silicon wafer.
3. preparation method according to claim 1 is characterized in that, the metal in the described metal level comprises: magnesium, titanium, hafnium or caesium.
4. preparation method according to claim 1 is characterized in that, the thickness range of described metal level is 2nm～20nm.
5. preparation method according to claim 1 is characterized in that, the thickness range of described anti-reflection layer is 50nm～80nm.
6. preparation method according to claim 1 is characterized in that, described P type silicon chip is monocrystalline silicon, polysilicon or quasi-monocrystalline silicon.
7. preparation method according to claim 1 is characterized in that, in described step b), adopts diffusion method or ion implantation to form the P-N knot at described P type front side of silicon wafer.
8. crystal silicon solar energy battery, described crystal silicon solar energy battery comprises from the bottom to top successively: back electrode/aluminium back surface field, P type silicon chip, P-N knot, metal level, anti-reflection layer and front electrode; It is characterized in that,
The barrier height that forms between described metal level and the N-type layer is less than the barrier height that forms between described positive electrode and the described N-type layer.
9. the preparation method of a crystal silicon solar energy battery, described method comprises the steps:
A) form matte in the front of N-type silicon chip;
B) form the N-P knot at described N-type front side of silicon wafer;
C) tie the formation metal level at described N-P;
D) form anti-reflection layer at described metal level;
E) form back electrode/aluminium back surface field at described N-type silicon chip back side;
F) form positive electrode at described N-type front side of silicon wafer;
It is characterized in that, the barrier height that forms between described metal level and the P type layer is less than the barrier height that forms between described positive electrode and the described P type layer.
10. preparation method according to claim 9 is characterized in that, in described step c), adopts thermal evaporation, magnetron sputtering or electro-plating method to form described metal level at described N-type front side of silicon wafer.
11. preparation method according to claim 9 is characterized in that, the metal in the described metal level comprises: magnesium, titanium, hafnium or caesium.
12. preparation method according to claim 9 is characterized in that, the thickness range of described metal level is 2nm～20nm.
13. a crystal silicon solar energy battery, described crystal silicon solar energy battery comprises from the bottom to top successively: back electrode/aluminium back surface field, N-type silicon chip, N-P knot, metal level, anti-reflection layer and front electrode; It is characterized in that,
The barrier height that forms between described metal level and the P type layer is less than the barrier height that forms between described positive electrode and the described P type layer.
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Cited By (3)
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| JP2017526164A (en) * | 2014-09-05 | 2017-09-07 | サンパワー コーポレイション | Improved front contact heterojunction processing |
| CN107394011A (en) * | 2017-08-16 | 2017-11-24 | 张家港协鑫集成科技有限公司 | Solar battery sheet and preparation method thereof |
| US10784383B2 (en) | 2015-08-07 | 2020-09-22 | E I Du Pont De Nemours And Company | Conductive paste composition and semiconductor devices made therewith |
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Application publication date: 20130918 |