CN102122684A - Electrode preparation method applied to crystalline silicon solar battery - Google Patents
Electrode preparation method applied to crystalline silicon solar battery Download PDFInfo
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- CN102122684A CN102122684A CN201110029997XA CN201110029997A CN102122684A CN 102122684 A CN102122684 A CN 102122684A CN 201110029997X A CN201110029997X A CN 201110029997XA CN 201110029997 A CN201110029997 A CN 201110029997A CN 102122684 A CN102122684 A CN 102122684A
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Abstract
The invention discloses an electrode preparation method applied to a crystalline silicon solar battery. The method comprises the following steps of: firstly, uniformly diffusing a silicon sheet and forming a p-n node and an oxidization layer rich in diffusion elements simultaneously; secondly, thinning and optimizing the thickness of the oxidization layer, covering a metal electrode on a part of the oxidization layer and performing thermal treatment, wherein in the thermal treatment process, the oxidization layer has functions of preventing the metal electrode from burning through the p-n node, and reducing the contact resistance of a metal semiconductor; and finally, removing the oxidization layer which is not covered by the metal electrode and a silicon material of which the surface of the silicon sheet is rich in diffusion elements by using chemical solution. By the method, the electrode can be prevented from burning through the p-n node and the contact resistance between the electrode and the silicon sheet can be reduced simultaneously, and the battery conversion efficiency can be improved; and the method has the advantage of low cost, and can be compatible with a process for industrially producing crystalline silicon solar batteries.
Description
Technical field
The invention belongs to technical field of solar cells, be specifically related to a kind of electrode preparation method that is applied to crystal-silicon solar cell.
Background technology
The manufacturing process of the conventional crystal silicon solar cell of suitability for industrialized production is at present: silicon chip cleans, and---------------PECVD deposits SiNx:H film---silk screen printing front, backplate and back of the body aluminium---high temperature co-firing knot to High temperature diffusion for plasma edge etching or corrosion back side p-n junction to remove phosphorosilicate glass in the matte preparation.Electrode can burn silicon nitride and emitter and forms alloy and contact in high temperature co-firing knot process, therefore in order to form the contact of good metal semiconductor, make and avoid electrode to burn emitter generation leaky when contact resistance is less, to the degree of depth of emitter and having relatively high expectations of emitter surface phosphorus doping density.Usually, after High temperature diffusion formed even emitter, its surface doping phosphorus atoms or boron atom dense was 10 with silicon chip for crystal-silicon solar cell
21～10
22Cm
-3Scope in.Auger recombination accounts for leading role under the high-dopant concentration situation of surface, causes electronics-hole-recombination phenomenon of producing on the top layer serious, and the short wave response of battery is relatively poor, and the short circuit current of battery descends; High surface doping concentration is unfavorable for the effect of surface passivation technology simultaneously, and the open circuit voltage of battery is difficult to get a promotion.Therefore the even emitter structure of conventional High temperature diffusion is unfavorable for the further raising of battery conversion efficiency.
At the shortcoming of even emitter structure, the technical study of new preparation selective emitting electrode structure becomes one of focus of high-efficiency crystal silicon solar cell technical study, and the improved electrode technology of preparing also is the research direction that addresses the above problem in addition.At present the preparation technology of selective emitter mainly comprises following several: twice diffusion method, slurry be diffusion method, laser heavy doping method and the mask method etc. of struggling against the corrosive influence altogether.Twice diffusion method relates to the diffusion process of twice high temperature, and not only cost of manufacture is higher, and the minority carrier life time of silicon chip and quality are descended; Slurry is total to the deficiency that diffusion method has effectively been avoided twice diffusion, but the cost of slurry is very high, and consumption is more, considers shortcoming to some extent from the economy aspect; The preparation cost height of laser heavy doping method is high to the stability and the controllability requirement of equipment such as laser; The struggle against the corrosive influence preparation cost of method of mask is lower; technology is simpler, but relates to the use of hydrofluoric acid/nitric acid, dangerous higher to environment and operating personnel; and the requirement of the controllability of etching process is very high, and the deposition of antiacid corrosion protection material and removal process are comparatively complicated.Therefore, these methods all have the shortcoming of self.Mainly comprise twice printing (Double Printing) technology, Aerosol jetting technology and plating (Plating) technology as for the improved electrode technology of preparing.Thereby twice printing technology effectively reduces the transmission resistance of electrode by the depth-width ratio that twice screen printing process can improve electrode, but do not solve contact resistance high and easily generating electrodes burn the problem of phenomenon; Aerosol jetting technology is the technology that German fraunhofer solar energy research is developed, this technology realizes the low contact resistance effect by meticulous being printed on the silicon chip that hangs down surface doping concentration, add electroplating technology and increase electrode, but this technical costs is very high, and is very high to the degree of dependence of equipment.
Therefore, develop a kind of low cost and with the electrode fabrication of existing suitability for industrialized production hardware compatibility, solve the above problems, further improve the efficient of crystal-silicon solar cell, seem particularly important.
Summary of the invention
The object of the present invention is to provide a kind of electrode preparation method that is applied to crystal-silicon solar cell, this method can effectively avoid the phenomenon that electrode burns p-n junction to produce, reduce the contact resistance of electrode and silicon chip simultaneously, improve battery conversion efficiency, have low-cost advantage and can with the industrialized production process of crystalline silicon solar battery compatibility, be fit to be applied in the large-scale industrial production.
The electrode preparation method that is applied to crystal-silicon solar cell provided by the invention is, at first silicon chip is evenly spread the oxide layer that forms p-n junction simultaneously and be rich in diffuse elements, then this thickness of oxide layer is carried out attenuate optimization, cover metal electrode in the part of oxide layer again, then heat-treat process, oxide layer plays the effect that the barrier metal electrode burns p-n junction and reduces the metal semiconductor contact resistance in the heat treatment process, uses chemical liquids to remove not the silicon materials that are rich in diffuse elements by the oxide layer of metal electrode overlay area and silicon chip surface at last.
Silicon chip of the present invention is p type or n type monocrystalline silicon piece or polysilicon chip, and silicon chip resistivity is 0.1～20 Ω cm, and thickness is 50～500 μ m.
Of the present inventionly be diffused as phosphorous diffusion or boron diffusion, the square resistance of diffusion is 30～120 Ω/.
The oxide layer that is rich in diffuse elements of the present invention is the silicon oxide layer that is rich in P elements or boron element, and thickness is 10～80nm.
Of the present inventionly oxidated layer thickness is carried out attenuate optimize the using plasma lithographic method or adopt hydrofluoric acid solution, ammonia spirit or tetramethyl ammonium hydroxide solution caustic solution, the thickness of attenuate rear oxidation layer is 5～50nm.
Metal electrode of the present invention is one or more the metal material that contains in silver, titanium, palladium, copper, aluminium, nickel, tin, the lead.
Metal electrode coverage mode of the present invention is a kind of mode in magnetron sputtering, hot evaporation, electron beam evaporation, the silk screen printing or the combination of several modes.
The maximum temperature of heat treatment process of the present invention is 700～1000 ℃, and the diffuse elements that oxide layer is rich in heat treatment process can diffuse in the silicon chip once more, and metal electrode and silicon form alloy structure simultaneously.
Chemical liquids of the present invention comprises acidic chemical liquid and alkali electroless liquid, wherein acidic chemical liquid is the mixed liquor of hydrofluoric acid solution or hydrofluoric acid and hydrochloric acid, sulfuric acid, and alkali electroless liquid is one or more the mixed liquor in potassium hydroxide solution, sodium hydroxide solution, solution of potassium carbonate, sodium carbonate liquor, ammonia spirit, the tetramethyl ammonium hydroxide solution.
Chemical liquids removing method of the present invention is to adopt acidic chemical liquid to remove not by the oxide layer of metal electrode overlay area earlier, adopts alkali electroless liquid to remove the silicon materials that diffuse elements is rich on the surface then, and the degree of depth of removed silicon materials is 5～100nm.
The invention has the beneficial effects as follows:
(1) the present invention adopts once evenly diffusion to form p-n junction and the oxide layer that is rich in diffuse elements simultaneously, this oxide layer is carried out thickness optimization, make oxide layer can prevent effectively that electrode from burning the phenomenon generation of p-n junction in high-temperature sintering process, play the anti-protective layer effect of burning, improve the battery yields of crystal-silicon solar cell suitability for industrialized production;
(2) the present invention adopts once evenly diffusion to form p-n junction and the oxide layer that is rich in diffuse elements simultaneously, utilize the characteristic that is rich in diffuse elements in the oxide layer, adopt heat treatment process to make diffuse elements diffuse into silicon chip once more, thereby effectively reduce the metal semiconductor contact resistance of electrode and silicon, improve the crystal-silicon solar cell photoelectric conversion efficiency;
(3) electrode preparation method that is applied to crystal-silicon solar cell provided by the invention has the advantage that technological process is simple, preparation cost is low, and can be well and the suitability for industrialized production hardware compatibility, is fit to be applied in the large-scale industrial production.
Embodiment
The present invention will be described below to enumerate specific embodiment.It is pointed out that following examples only are used for that the invention will be further described, do not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
The electrode preparation method that is applied to crystal-silicon solar cell that following examples are mentioned is, at first silicon chip is evenly spread the oxide layer that forms p-n junction simultaneously and be rich in diffuse elements, then this thickness of oxide layer is carried out attenuate optimization, cover metal electrode in the part of oxide layer again, then heat-treat process, oxide layer plays the effect that the barrier metal electrode burns p-n junction and reduces the metal semiconductor contact resistance in the heat treatment process, use chemical liquids to remove not the silicon materials that are rich in diffuse elements by the oxide layer of metal electrode overlay area and silicon chip surface at last, when can avoiding electrode to burn p-n junction, the method reduces the contact resistance of electrode and silicon chip, improve battery conversion efficiency, have low-cost advantage and can with the industrialized production process of crystalline silicon solar battery compatibility.
Embodiment 1
A kind of electrode preparation method that is applied to crystal-silicon solar cell of mentioning in the present embodiment may further comprise the steps:
(1) silicon chip is carried out the oxide layer that high temperature phosphorous diffuses to form uniform p-n junction and is rich in P elements;
(2) this thickness of oxide layer is carried out attenuate optimization;
(3) cover the argentiferous metal electrode in the part of oxide layer;
(4) silicon chip, oxide layer and argentiferous metal electrode are heat-treated process;
(5) adopt chemical liquids to remove not by the oxide layer of metal electrode overlay area and the silicon materials that are rich in P elements.
The described silicon chip of present embodiment is a p type monocrystalline silicon piece, and silicon chip resistivity is 1.5 Ω cm, and silicon wafer thickness is 200 μ m.
The highest diffusion temperature of the described high temperature phosphorous diffusion of present embodiment is 870 ℃.
The hydrofluoric acid solution caustic solution of weight concentration 5% is adopted in the described attenuate optimization to oxidated layer thickness of present embodiment, and the oxidated layer thickness behind the attenuate is about 20nm.
The described local of present embodiment is covered as and utilizes screen printing mode to cover " H " type electrode pattern.
The maximum temperature of the described heat treatment process of present embodiment is 850 ℃.
The described chemical liquids of present embodiment comprises hydrofluoric acid solution and tetramethyl ammonium hydroxide solution.
The described chemical liquids removing method of present embodiment is at first to adopt the hydrofluoric acid solution of weight concentration 5% to remove the oxide layer be rich in P elements to adopt the tetramethyl ammonium hydroxide solution of weight concentration 20% to remove the silicon materials that are rich in P elements that the degree of depth is about 50nm then.
Embodiment 2
A kind of electrode preparation method that is applied to crystal-silicon solar cell of mentioning in the present embodiment may further comprise the steps:
(1) silicon chip is carried out the oxide layer that high temperature phosphorous diffuses to form uniform p-n junction and is rich in P elements;
(2) this thickness of oxide layer is carried out attenuate optimization;
(3) cover the argentiferous metal electrode in the part of oxide layer;
(4) silicon chip, oxide layer and argentiferous metal electrode are heat-treated process;
(5) adopt chemical liquids to remove not by the oxide layer of metal electrode overlay area and the silicon materials that are rich in P elements.
The described silicon chip of present embodiment is a p type polysilicon chip, and silicon chip resistivity is 1.5 Ω cm, and silicon wafer thickness is 200 μ m.
The highest diffusion temperature of the described high temperature phosphorous diffusion of present embodiment is 850 ℃.
The hydrofluoric acid solution caustic solution of weight concentration 5% is adopted in the described attenuate optimization to oxidated layer thickness of present embodiment, and the oxidated layer thickness behind the attenuate is about 20nm.
The described local of present embodiment is covered as and utilizes screen printing mode to cover " H " type electrode pattern.
The maximum temperature of the described heat treatment process of present embodiment is 850 ℃.
The described chemical liquids of present embodiment comprises hydrofluoric acid solution and tetramethyl ammonium hydroxide solution.
The described chemical liquids removing method of present embodiment is at first to adopt the hydrofluoric acid solution of weight concentration 5% to remove the oxide layer be rich in P elements to adopt the tetramethyl ammonium hydroxide solution of weight concentration 20% to remove the silicon materials that are rich in P elements that the degree of depth is about 30nm then.
Embodiment 3
A kind of electrode preparation method that is applied to crystal-silicon solar cell of mentioning in the present embodiment may further comprise the steps:
(1) silicon chip is carried out the oxide layer that the high temperature boron diffusion forms uniform p-n junction and is rich in boron element;
(2) this thickness of oxide layer is carried out attenuate optimization;
(3) cover the argentiferous metal electrode in the part of oxide layer;
(4) silicon chip, oxide layer and argentiferous metal electrode are heat-treated process;
(5) adopt chemical liquids to remove not by the oxide layer of metal electrode overlay area and the silicon materials that are rich in boron element.
The described silicon chip of present embodiment is a n type monocrystalline silicon piece, and silicon chip resistivity is 1.5 Ω cm, and silicon wafer thickness is 200 μ m.
The highest diffusion temperature of the described high temperature boron diffusion of present embodiment is 870 ℃.
The hydrofluoric acid solution caustic solution of weight concentration 5% is adopted in the described attenuate optimization to oxidated layer thickness of present embodiment, and the oxidated layer thickness behind the attenuate is about 20nm.
The described local of present embodiment is covered as and utilizes screen printing mode to cover " H " type electrode pattern.
The maximum temperature of the described heat treatment process of present embodiment is 850 ℃.
The described chemical liquids of present embodiment comprises hydrofluoric acid solution and tetramethyl ammonium hydroxide solution.
The described chemical liquids removing method of present embodiment is at first to adopt the hydrofluoric acid solution of weight concentration 5% to remove the oxide layer be rich in boron element to adopt the tetramethyl ammonium hydroxide solution of weight concentration 20% to remove the silicon materials that are rich in boron element that the degree of depth is about 50nm then.
Embodiment 4
A kind of electrode preparation method that is applied to crystal-silicon solar cell of mentioning in the present embodiment may further comprise the steps:
(1) silicon chip is carried out the oxide layer that the high temperature boron diffusion forms uniform p-n junction and is rich in boron element;
(2) this thickness of oxide layer is carried out attenuate optimization;
(3) cover the argentiferous metal electrode in the part of oxide layer;
(4) silicon chip, oxide layer and argentiferous metal electrode are heat-treated process;
(5) adopt chemical liquids to remove not by the oxide layer of metal electrode overlay area and the silicon materials that are rich in boron element.
The described silicon chip of present embodiment is a n type polysilicon chip, and silicon chip resistivity is 2.5 Ω cm, and silicon wafer thickness is 300 μ m.
The highest diffusion temperature of the described high temperature boron diffusion of present embodiment is 850 ℃.
The described attenuate to oxidated layer thickness of present embodiment is optimized the using plasma lithographic method, and the oxidated layer thickness behind the attenuate is about 30nm.
The described local of present embodiment is covered as and utilizes screen printing mode to cover " H " type electrode pattern.
The maximum temperature of the described heat treatment process of present embodiment is 850 ℃.
The described chemical liquids of present embodiment comprises hydrofluoric acid solution and tetramethyl ammonium hydroxide solution.
The described chemical liquids removing method of present embodiment is at first to adopt the hydrofluoric acid solution of weight concentration 5% to remove the oxide layer be rich in boron element to adopt the tetramethyl ammonium hydroxide solution of weight concentration 20% to remove the silicon materials that are rich in boron element that the degree of depth is about 30nm then.
Embodiment 5
A kind of electrode preparation method that is applied to crystal-silicon solar cell of mentioning in the present embodiment may further comprise the steps:
(1) silicon chip is carried out the oxide layer that the high temperature boron diffusion forms uniform p-n junction and is rich in boron element;
(2) this thickness of oxide layer is carried out attenuate optimization;
(3) cover the argentiferous metal electrode in the part of oxide layer;
(4) silicon chip, oxide layer and argentiferous metal electrode are heat-treated process;
(5) adopt chemical liquids to remove not by the oxide layer of metal electrode overlay area and the silicon materials that are rich in boron element.
The described silicon chip of present embodiment is a n type polysilicon chip, and silicon chip resistivity is 2.5 Ω cm, and silicon wafer thickness is 300 μ m.
The highest diffusion temperature of the described high temperature boron diffusion of present embodiment is 870 ℃.
The described attenuate to oxidated layer thickness of present embodiment is optimized the using plasma lithographic method, and the oxidated layer thickness behind the attenuate is about 30nm.
The described local of present embodiment is covered as and utilizes screen printing mode to cover " H " type electrode pattern.
The maximum temperature of the described heat treatment process of present embodiment is 870 ℃.
The described chemical liquids of present embodiment comprises hydrofluoric acid solution and sodium hydroxide solution.
The described chemical liquids removing method of present embodiment is at first to adopt the hydrofluoric acid solution of weight concentration 5% to remove the oxide layer be rich in boron element to adopt the sodium hydroxide solution of weight concentration 20% to remove the silicon materials that are rich in boron element that the degree of depth is about 30nm then.
Claims (10)
1. electrode preparation method that is applied to crystal-silicon solar cell, it is characterized in that, at first silicon chip is evenly spread the oxide layer that forms p-n junction simultaneously and be rich in diffuse elements, then this thickness of oxide layer is carried out attenuate optimization, cover metal electrode in the part of oxide layer again, then heat-treat process, oxide layer plays the effect that the barrier metal electrode burns p-n junction and reduces the metal semiconductor contact resistance in the heat treatment process, uses chemical liquids to remove not the silicon materials that are rich in diffuse elements by the oxide layer of metal electrode overlay area and silicon chip surface at last.
2. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1 is characterized in that, described silicon chip is p type or n type monocrystalline silicon piece or polysilicon chip, and silicon chip resistivity is 0.1～20 Ω cm, and thickness is 50～500 μ m.
3. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1 is characterized in that, describedly evenly is diffused as phosphorous diffusion or boron diffusion, and the square resistance of diffusion is 30～120 Ω/.
4. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1 is characterized in that, the described oxide layer that is rich in diffuse elements is the silicon oxide layer that is rich in P elements or boron element, and thickness is 10～80nm.
5. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1, it is characterized in that, describedly oxidated layer thickness is carried out attenuate optimize the using plasma lithographic method or adopt hydrofluoric acid solution, ammonia spirit or tetramethyl ammonium hydroxide solution caustic solution, the thickness of attenuate rear oxidation layer is 5～50nm.
6. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1 is characterized in that, described metal electrode is one or more the metal material that contains in silver, titanium, palladium, copper, aluminium, nickel, tin, the lead.
7. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1 is characterized in that, described metal electrode coverage mode is a kind of mode in magnetron sputtering, hot evaporation, electron beam evaporation, the silk screen printing or the combination of several modes.
8. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1, it is characterized in that, the maximum temperature of described heat treatment process is 700～1000 ℃, the diffuse elements that is rich in the oxide layer in heat treatment process diffuses in the silicon chip once more, and metal electrode and silicon form alloy structure simultaneously.
9. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1, it is characterized in that, described chemical liquids comprises acidic chemical liquid and alkali electroless liquid, wherein acidic chemical liquid is the mixed liquor of hydrofluoric acid solution or hydrofluoric acid and hydrochloric acid, sulfuric acid, and alkali electroless liquid is one or more the mixed liquor in potassium hydroxide solution, sodium hydroxide solution, solution of potassium carbonate, sodium carbonate liquor, ammonia spirit, the tetramethyl ammonium hydroxide solution.
10. the electrode preparation method that is applied to crystal-silicon solar cell according to claim 1, it is characterized in that, described chemical liquids removing method is to adopt acidic chemical liquid to remove not by the oxide layer of metal electrode overlay area earlier, adopt alkali electroless liquid to remove the silicon materials that diffuse elements is rich on the surface then, the degree of depth of removed silicon materials is 5～100nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112802926A (en) * | 2021-04-13 | 2021-05-14 | 浙江晶科能源有限公司 | Solar cell preparation method and semiconductor structure |
| CN114589466A (en) * | 2022-03-22 | 2022-06-07 | 中山大学 | Method for preparing three-dimensional microneedle blood glucose electrode based on dimensionality reduction screen printing |
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| EP1921683A2 (en) * | 2006-10-30 | 2008-05-14 | Shin-Etsu Chemical Co., Ltd. | Method for producing single crystal silicon solar cell and single crystal silicon solar cell |
| US20090162972A1 (en) * | 2007-12-21 | 2009-06-25 | Palo Alto Research Center Incorporated | Metallization contact structures and methods for forming multiple-layer electrode structures for silicon solar cells |
| CN101840955A (en) * | 2009-03-18 | 2010-09-22 | 中国科学院微电子研究所 | Preparation method of crystalline silicon solar cell based on superlattice structure of silicon quantum dot |
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| EP1921683A2 (en) * | 2006-10-30 | 2008-05-14 | Shin-Etsu Chemical Co., Ltd. | Method for producing single crystal silicon solar cell and single crystal silicon solar cell |
| US20090162972A1 (en) * | 2007-12-21 | 2009-06-25 | Palo Alto Research Center Incorporated | Metallization contact structures and methods for forming multiple-layer electrode structures for silicon solar cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112802926A (en) * | 2021-04-13 | 2021-05-14 | 浙江晶科能源有限公司 | Solar cell preparation method and semiconductor structure |
| CN112802926B (en) * | 2021-04-13 | 2021-08-24 | 浙江晶科能源有限公司 | Solar cell preparation method and semiconductor structure |
| CN114589466A (en) * | 2022-03-22 | 2022-06-07 | 中山大学 | Method for preparing three-dimensional microneedle blood glucose electrode based on dimensionality reduction screen printing |
| CN114589466B (en) * | 2022-03-22 | 2023-08-15 | 中山大学 | Method for preparing three-dimensional microneedle blood sugar electrode based on dimension reduction screen printing |
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