CN103247720A - Method for preparing crystalline silicon heterojunction solar cells - Google Patents
Method for preparing crystalline silicon heterojunction solar cells Download PDFInfo
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- CN103247720A CN103247720A CN2013101712776A CN201310171277A CN103247720A CN 103247720 A CN103247720 A CN 103247720A CN 2013101712776 A CN2013101712776 A CN 2013101712776A CN 201310171277 A CN201310171277 A CN 201310171277A CN 103247720 A CN103247720 A CN 103247720A
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Abstract
The invention discloses a method for preparing crystalline silicon heterojunction solar cells, which comprises the following steps: (1) conducting cleaning and corrosion for making texture surface; (2) conducting Si ion implantation to the front surface and the back surface of the silicon wafer, and forming a layer of amorphous silicon membrane on the front surface and the back surface respectively; (3) conducting twice B ion implantation to the amorphous silicon membrane on the front surface of the silicon wafer; (4) conducting B ion implantation to the amorphous silicon membrane on the back surface of the silicon wafer; (5) conducting P ion implantation to the amorphous silicon membrane on the back surface of the silicon wafer;(6) conducting thermal activation processing; and (7) arranging conductive film layers on the front surface and the back surface of the silicon wafer respectively, and (8) conducting silk screen printing sintering in silicon wafer surface and preparing metal electrode. By adopting the method provided by the invention, high quality crystal silicon heterojunction solar cells are obtained, high quality amorphous silicon thin film layer and the superposition interface of the integral crystalline silicon and amorphous silicon heterojunction with few defects are formed, passivation effect is improved, and the leak current is decreased effectively.
Description
Technical field
The present invention relates to a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, belong to technical field of solar.
Background technology
Along with the extensive use of solar module, photovoltaic generation more and more occupies important proportion in new forms of energy, obtained develop rapidly.In the present business-like solar cell product, the market share maximum of crystalline silicon (monocrystalline and polycrystalline) solar cell keeps the occupation rate of market more than 85% always.Therefore, the crystal silicon solar energy battery of research and development high performance-price ratio still is one of R﹠D direction of various countries researcher.
At present, Japanese Sanyo company has produced a kind of silicon/crystalline silicon heterogenous joint solar cell.So-called heterojunction, the PN junction that refers to battery front side is to be made of amorphous silicon and n type single crystal silicon substrate, amorphous silicon layer comprises P type amorphous silicon membrane layer and intrinsic amorphous silicon thin layer; Then constitute back surface field by intrinsic amorphous silicon thin layer and N-type amorphous silicon membrane layer at cell backside.Amorphous silicon is as the direct gap semiconductor material, and is bigger to the absorption of incident light coefficient, and the amorphous silicon membrane layer of very little thickness can absorb the incident light of considerable part; Simultaneously, the energy gap of amorphous silicon is 1.7eV, and much larger than the energy gap 1.1eV of crystalline silicon, therefore, the open circuit voltage of the solar cell of heterojunction structure can be significantly higher than conventional crystal silicon solar energy battery, thereby has brought excellent performance performance.The technological process of Sanyo company production heterojunction solar battery is roughly as follows: at first the surface of n type single crystal silicon silicon chip is carried out corroding making herbs into wool after the wet chemical process cleaning, form micron order pyramid suede structure at its front and back; Then use the PECVD method to form the heterojunction emitter at silicon chip positive deposition one deck intrinsic amorphous silicon film and one deck P type amorphous silicon membrane, form back of the body electric field at silicon chip backside deposition one deck intrinsic amorphous silicon film and the heavily doped N-type amorphous silicon membrane of one deck; Then at silicon chip tow sides deposit transparent conductive film; Use silk screen printing and sintering to prepare metal electrode at silicon chip surface at last, obtain complete silicon/crystalline silicon heterogenous joint solar cell.
Yet in the above processing step, the wet-chemical cleaning of the silicon chip surface of the first step is very crucial.This is all very little because of the thickness of the multi-layer amorphous silicon film that next uses the PECVD deposition, be nanoscale, so the clean-up performance to silicon chip surface requires very high, any impurity or dust granule all can become the fault of construction of heterojunction, have a strong impact on the interface state density of battery, influence the open circuit voltage of battery.Therefore, present industrial general employing multiple tracks chemical solution and the treatment fluid mode of cleaning repeatedly.Yet this method not only causes cost to raise, and operation is tediously long, and effect can't be guaranteed, and has also produced environmental problems such as liquid waste processing.In addition, adopt in the process of PECVD sedimentation structure heterojunction, cause point discharge easily, influence the amorphous silicon membrane quality, greatly reduce yields.
Therefore, develop a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell, to prepare high-quality silicon/crystalline silicon heterogenous joint solar cell, have active operation significance.
Summary of the invention
The object of the invention provides a kind of silicon/crystalline silicon heterogenous joint solar cell.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell comprises the steps:
(1) the n type single crystal silicon silicon chip is carried out surface chemistry and clean, corrode making herbs into wool;
(2) front and back with above-mentioned silicon chip carries out the injection of Si ion respectively, forms one deck amorphous silicon membrane on tow sides respectively;
(3) amorphous silicon membrane with above-mentioned silicon chip front carries out twice B ion injection;
(4) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of B ion;
(5) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of P ion;
(6) above-mentioned doped amorphous silicon film being carried out hot activation handles;
(7) tow sides at above-mentioned silicon chip arrange the transparent conductive film layer;
(8) silk screen printing, sintering prepare metal electrode at silicon chip surface, can obtain silicon/crystalline silicon heterogenous joint solar cell.
Above, the Si ion in the described step (2) injects and uses disilane or other silane based gas to make ion source.
B ion in described step (3) and the step (4) injects can use diborane, and boron trifluoride or other boron-containing gas are made ion source.
Hot activation in the described step (6) is handled and can be adopted annealing furnace annealing or rapid thermal annealing method.The purpose of hot activation treatment process is to eliminate lattice damage, and makes foreign atom occupy lattice position and be activated.
The transparent conductive film layer can adopt the method preparation of reactive plasma deposition or magnetron sputtering in the described step (7), and transparent conductive film can use ITO, IZO, and one or more in the IWO material deposit separately or codeposition.Preferable methods is the reactive plasma sedimentation, because this method is to the surface damage minimum of substrate.Described transparent conductive film layer plays the antireflective effect simultaneously.
In the described step (1), the pyramid suede structure that corrosion making herbs into wool forms, its pyramid size is controlled usually at 5 to 20 microns.Usually can use matte processing means such as alkaline corrosion to carry out smooth rounding when forming described pyramid suede structure and handle, to reach the purpose of removing burr and pinnacle.
In the step (3), the amorphous silicon membrane in above-mentioned silicon chip front is carried out twice B ion inject, thereby form P type amorphous silicon membrane layer at the intrinsic amorphous silicon thin layer, so far formed in the front of above-mentioned silicon chip
P/i/NThe heterojunction of structure.In the step (4), the amorphous silicon membrane at the above-mentioned silicon chip back side is carried out the B ion inject, thereby make the bottom of N-type amorphous silicon membrane or Zone Full be transformed into the intrinsic amorphous silicon thin layer; In the step (5), the amorphous silicon membrane at the above-mentioned silicon chip back side is carried out the P ion inject, thereby form N+ type amorphous silicon layer on the top layer of amorphous silicon membrane, so far formed in above-mentioned silicon chip back
N/i/N+The heterojunction of structure.
In described step (3), (4) and (5), can inject energy of ions by control, concentration and duration reach the degree of depth that accurate control ion injects, the distribution of doping content and doping ion.
In the technique scheme, the thickness of the amorphous silicon membrane in the described step (2) is 2 ~ 30 nm.
In the technique scheme, the degree of depth of B ion injection for the first time is 1 ~ 30 nm in the described step (3), and the degree of depth of B ion injection for the second time is 1 ~ 15 nm.
In the technique scheme, the degree of depth that the B ion injects in the described step (4) is 1 ~ 30nm.
In the technique scheme, the degree of depth that the P ion injects in the described step (5) is 1 ~ 15nm.
Another kind of technical scheme correspondingly, a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell comprises the steps:
(1) the p type single crystal silicon silicon chip is carried out surface chemistry and clean, corrode making herbs into wool;
(2) front and back with above-mentioned silicon chip carries out the injection of Si ion respectively, forms one deck amorphous silicon membrane on tow sides respectively;
(3) amorphous silicon membrane with above-mentioned silicon chip front carries out twice P ion injection;
(4) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of P ion;
(5) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of B ion;
(6) above-mentioned doped amorphous silicon film being carried out hot activation handles;
(7) tow sides at above-mentioned silicon chip arrange the transparent conductive film layer;
(8) silk screen printing, sintering prepare metal electrode at silicon chip surface, can obtain silicon/crystalline silicon heterogenous joint solar cell.
In the technique scheme, the thickness of the amorphous silicon membrane in the described step (2) is 2 ~ 30 nm.
In the technique scheme, the degree of depth of P ion injection for the first time is 1 ~ 30 nm in the described step (3), and the degree of depth of P ion injection for the second time is 1 ~ 15 nm.
In the technique scheme, the degree of depth that the P ion injects in the described step (4) is 1 ~ 30nm.
In the technique scheme, the degree of depth that the B ion injects in the described step (5) is 1 ~ 15nm.
Because the employing of technique scheme, compared with prior art, the present invention has following advantage:
1. the present invention has developed a kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell newly, use ion implantation to substitute traditional PECVD sedimentation and prepare heterojunction structure in the silicon/crystalline silicon heterogenous junction battery, integrated crystal silicon, the non crystal heterogeneous agglomeration stack interface of high-quality amorphous silicon membrane layer and few defective have been formed, improve passivation effect and reduced leakage current effectively, obtained high-quality silicon/crystalline silicon heterogenous joint solar cell.
2. method of the present invention has reduced the requirement to the silicon chip surface chemically cleaning significantly, therefore adopts conventional cleaning and texturing technology can obtain the heterojunction battery of stay in grade, has good versatility.
3. the present invention can inject the degree of depth, doping content, the distribution of doping ion and the thickness of each thin layer that accurate control of energy of ions, concentration and time ion injects by control, guarantee the precision of heterojunction structure in the battery, thereby obtain high-quality battery emitter, improve the open circuit voltage of battery, effectively promoted the transformation efficiency of battery.
4. preparation method of the present invention is simple, and cost is low, is suitable for suitability for industrialized production.
Embodiment
Be further described below in conjunction with the present invention of embodiment:
Embodiment one
A kind of preparation method of silicon/crystalline silicon heterogenous joint solar cell comprises the steps:
The first step is carried out chemical surface with the n type single crystal silicon silicon chip and is cleaned;
Second step, above-mentioned silicon chip is corroded making herbs into wool, form micron order pyramid suede structure at its front and back;
Usually can use matte processing means such as alkaline corrosion to carry out smooth rounding when forming described pyramid suede structure and handle, to reach the purpose of removing burr and pinnacle;
The 3rd step, adopt ion implantation, at the front and back injection Si of above-mentioned silicon chip ion, thereby respectively form the thick amorphous silicon membrane of 2 ~ 30 nm in the silicon chip upper and lower surface;
The 4th step, adopt ion implantation, the bottom of the amorphous silicon membrane in silicon chip front is carried out B ion injection first time, thereby form the intrinsic amorphous silicon thin layer of 1 ~ 15 nm; Carry out the B ion injection second time again, thereby form the P type amorphous silicon membrane layer of 1 ~ 15 nm on the top layer of amorphous silicon membrane; So far formed in the front of above-mentioned silicon chip
P/i/NThe heterojunction of structure;
The 5th step, adopt ion implantation, the amorphous silicon membrane at the silicon chip back side is carried out the B ion inject, thereby form the intrinsic amorphous silicon thin layer of 1 ~ 15 nm at the bottom of amorphous silicon membrane;
In the 6th step, this amorphous silicon membrane layer is carried out the injection of P ion, thereby form the N+ type amorphous silicon layer of 1 ~ 15 nm thickness on the top layer of amorphous silicon membrane; So far formed in above-mentioned silicon chip back
N/i/N+The heterojunction of structure;
The 7th step, adopt annealing furnace annealing or rapid thermal annealing method, carry out the amorphous silicon membrane that the overdoping ion injects and carry out activating process above-mentioned, activating process can be eliminated lattice damage, and makes foreign atom occupy lattice position and be activated;
In the 8th step, utilize the method for reactive plasma deposition or magnetron sputtering at the thick transparent conductive film layer of surface preparation 50 ~ 200 nm of above-mentioned silicon chip;
Described transparent conductive film can use ITO, IZO, and one or more in the materials such as IWO carry out codeposition;
The 9th step, adopt silk screen printing and sintering or electric plating method to form the front and back metal electrode, can obtain described silicon/crystalline silicon heterogenous joint solar cell;
When adopting method for printing screen, can optimize the pictorial pattern of metal gates and the performance that depth-width ratio improves battery;
When adopting electro-plating method, can adopt means help formation metal electrodes such as mask lithography technology; The material of metal gates can be Ag, Cu, Al or other metal.
Above embodiment is only unrestricted in order to technical scheme of the present invention to be described.The present invention can be used for the heterojunction solar battery based on the p type single crystal silicon sheet equally, or the manufacturing of various solar cells such as the silicon heterogenous battery of pedion (pedia).Those of ordinary skill in the art should be appreciated that and can make amendment or be equal to replacement technical scheme of the present invention, and do not break away from the spiritual scope of technical solution of the present invention, and it all should be encompassed in the middle of the claim scope of the present invention.
Claims (10)
1. the preparation method of a silicon/crystalline silicon heterogenous joint solar cell is characterized in that, comprises the steps:
(1) the n type single crystal silicon silicon chip is carried out surface chemistry and clean, corrode making herbs into wool;
(2) front and back with above-mentioned silicon chip carries out the injection of Si ion respectively, forms one deck amorphous silicon membrane on tow sides respectively;
(3) amorphous silicon membrane with above-mentioned silicon chip front carries out twice B ion injection;
(4) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of B ion;
(5) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of P ion;
(6) above-mentioned doped amorphous silicon film being carried out hot activation handles;
(7) tow sides at above-mentioned silicon chip arrange the transparent conductive film layer;
(8) silk screen printing, sintering prepare metal electrode at silicon chip surface, can obtain silicon/crystalline silicon heterogenous joint solar cell.
2. preparation method according to claim 1, it is characterized in that: the thickness of the amorphous silicon membrane in the described step (2) is 2 ~ 30 nm.
3. preparation method according to claim 1 is characterized in that: in the described step (3) for the first time the degree of depth injected of B ion be 1 ~ 30 nm, the degree of depth injected of B ion is 1 ~ 15 nm for the second time.
4. preparation method according to claim 1 is characterized in that: the degree of depth that the B ion injects in the described step (4) is 1 ~ 30nm.
5. preparation method according to claim 1 is characterized in that: the degree of depth that the P ion injects in the described step (5) is 1 ~ 15nm.
6. the preparation method of a silicon/crystalline silicon heterogenous joint solar cell is characterized in that, comprises the steps:
(1) the p type single crystal silicon silicon chip is carried out surface chemistry and clean, corrode making herbs into wool;
(2) front and back with above-mentioned silicon chip carries out the injection of Si ion respectively, forms one deck amorphous silicon membrane on tow sides respectively;
(3) amorphous silicon membrane with above-mentioned silicon chip front carries out twice P ion injection;
(4) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of P ion;
(5) amorphous silicon membrane with the above-mentioned silicon chip back side carries out the injection of B ion;
(6) above-mentioned doped amorphous silicon film being carried out hot activation handles;
(7) tow sides at above-mentioned silicon chip arrange the transparent conductive film layer;
(8) silk screen printing, sintering prepare metal electrode at silicon chip surface, can obtain silicon/crystalline silicon heterogenous joint solar cell.
7. preparation method according to claim 6, it is characterized in that: the thickness of the amorphous silicon membrane in the described step (2) is 2 ~ 30 nm.
8. preparation method according to claim 6 is characterized in that: in the described step (3) for the first time the degree of depth injected of P ion be 1 ~ 30 nm, the degree of depth injected of P ion is 1 ~ 15 nm for the second time.
9. preparation method according to claim 6 is characterized in that: the degree of depth that the P ion injects in the described step (4) is 1 ~ 30nm.
10. preparation method according to claim 6 is characterized in that: the degree of depth that the B ion injects in the described step (5) is 1 ~ 15nm.
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| CN105070789A (en) * | 2015-08-20 | 2015-11-18 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of emitter electrode of crystalline silica solar cell |
| CN106571411A (en) * | 2016-10-19 | 2017-04-19 | 苏州阿特斯阳光电力科技有限公司 | Crystal silicon wafer etching method |
| CN109768102A (en) * | 2018-12-27 | 2019-05-17 | 浙江师范大学 | A kind of silicon/crystalline silicon heterogenous joint solar cell and preparation method thereof |
| CN115241327A (en) * | 2022-08-26 | 2022-10-25 | 共青城辟微自动化有限公司 | Crystalline silicon solar cell prepared through annealing crystallization and preparation method thereof |
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| CN105070789A (en) * | 2015-08-20 | 2015-11-18 | 苏州阿特斯阳光电力科技有限公司 | Preparation method of emitter electrode of crystalline silica solar cell |
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| CN115241327A (en) * | 2022-08-26 | 2022-10-25 | 共青城辟微自动化有限公司 | Crystalline silicon solar cell prepared through annealing crystallization and preparation method thereof |
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