CN103078001A - Manufacturing method of silicon-based thin-film laminated solar battery - Google Patents
Manufacturing method of silicon-based thin-film laminated solar battery Download PDFInfo
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- CN103078001A CN103078001A CN2012105785108A CN201210578510A CN103078001A CN 103078001 A CN103078001 A CN 103078001A CN 2012105785108 A CN2012105785108 A CN 2012105785108A CN 201210578510 A CN201210578510 A CN 201210578510A CN 103078001 A CN103078001 A CN 103078001A
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Abstract
The invention discloses a manufacturing method of a silicon-based thin-film laminated solar battery, and the method is characterized in that an electrically-conductive nanometer silicon-oxide or silicon-carbide thin film is introduced into n layers of a bottom battery of a single-junction or multi-junction p/i/n-type silicon-based thin-film solar battery to form an n-type doped layer of a multilayer composite thin film, and silicon and silicon-oxide (SiOx) or silicon carbide (SiCx) doping, crystalline fraction, thickness, refraction index and electric conductivity in the n layers are adjusted and optimized simultaneously. According to the novel n-layer composite structure, the back reflection is increased and the n-layer optical absorption of the doped layer is reduced, so that the photoelectric conversion efficiency of the silicon thin-film laminated solar battery can be effectively increased.
Description
Technical field
The present invention relates to the photovoltaic solar cell technical field, particularly a kind of manufacture method of silicon-based thin-film lamination solar cell.
Background technology
Along with the worsening shortages of the energy, people pay attention to increasingly to the development and utilization of solar energy.Market is to more large tracts of land, the demand lighter and thinner and novel solar battery that production cost is lower increase day by day.In the photovoltaic cell field, silicon-based thin film solar cell is abundant, pollution-free because of its raw material reserves, preparation technology is simple, be convenient to the advantage such as large tracts of land serialization production, is subject to extensive concern.In the silicon-base thin-film battery, amorphous silicon film battery has the effect of photo attenuation, needs to realize by the thickness of attenuate battery the photo attenuation of inhibition amorphous silicon film battery on the technique; The microcrystalline silicon film battery, usually the required thickness of battery needs long preparation time and material consumption at the 1-2 micron, for reducing cost of material and improving production capacity, also is badly in need of the thickness of attenuate microcrystalline silicon film.But the attenuate of hull cell thickness can reduce battery to sun Optical Absorption, thereby reduces the efficient of hull cell.
In order to increase the light path of light in solar cell, make light absorption increase the light trapping structure that need to add.Light trapping structure is the matte composite back electrode of utilizing the front electrode of matte and high reflection, by processes such as reflection of light, refraction and scatterings, incident light is disperseed and be limited in the battery, it is is repeatedly come and gone absorbs, increase the light path of light in solar cell, light absorption is increased, and battery conversion efficiency improves.Yet, all sunlight there is certain absorption owing to have front electrode, zinc oxide and the metal back electrode of matte itself, suede structure has also strengthened front electrode, zinc oxide and metal back electrode to the absorption of light simultaneously, thereby has limited the raising of hull cell efficient.Especially metal back electrode, on the one hand, the surface that metal electrode contacts with zinc oxide has the phenomenon of certain surface atomizing, has reduced the albedo of metal electrode to sunlight.And adopt the metal back electrode with suede structure, further reduced the reflectivity of metal back electrode to sunlight.Therefore, how to increase back reflection, help further to improve the efficient of hull cell.
In thin film silicon solar cell, the doped layer of p-type and N-shaped is called as " dead band ", to not contribution of photogenerated current, in order to improve the efficient of battery, answers the light absorption in the reduce doped layer.But in light trapping structure, repeatedly come and go because incident light is limited in the battery, can cause doped layer to the absorption of wide amount.Clearly, reduce doped layer to Optical Absorption, generally will reduce as far as possible the thickness of dead layer, i.e. the thickness of attenuate doped layer.The thickness that too reduces heavily doped layer is the n layer particularly, will cause the tunnel effect between intrinsic layer and back electrode conductor, thereby reduce the height of effective potential barrier but on the other hand.From the open circuit voltage angle, doped layer must be enough thick, in order to the Fermi level of this layer " lock " is lived.Therefore, the suitable N-shaped doped layer of design is a major issue.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of silicon-based thin-film lamination solar cell, can further improve the photoelectric conversion efficiency of silicon-based thin-film lamination solar cell.
The manufacture method of silicon-based thin-film lamination solar cell of the present invention comprises:
Deposit transparent conductive oxide film on transparency carrier;
Deposit successively anodal p1 layer, electric layer i1 and the negative pole n1 layer of the first battery on described transparent conductive oxide film surface; And/or
At anodal p2 layer, electric layer i2 and the negative pole n2 layer of surface deposition second battery of described the first battery, form the dual stack battery; And/or
Anodal p3 layer, electric layer i3 and negative pole n3 layer at the further deposition of described the second battery surface the 3rd battery form three lamination batteries;
Wherein,
In the nano-silicon n of crystallization layer, introduce nanometer silica SiOx or the silicon-carbon SiCx film of conduction, form the N-shaped doped layer of multi-layer compound film;
At battery surface depositing electrically conductive thin film back electrode;
Carry out laminating packaging and subsequent treatment.
Described nano-silicon n layer comprises n1 layer or n2 layer or n3 layer.
Described nano-silicon n layer is the multi-layer compound structure of crystallization microcrystal silicon and crystallite silica.
Multi-layer compound structure is SiOx/Si, or SiOx/Si/SiOx, or Si/SiOx/Si, or SiOx/Si/SiOx/Si, or SiOx/Si/SiOx/Si/SiOx, or SiCx/Si, or SiCx/Si/SiCx, or Si/SiCx/Si, or the SiCx/Si/SiCx/Si structure.
SiOx or SiCx are the conductive layer of the crystallization of doping in the described multi-layer compound structure, and crystallization rate is at 20-70%, and thickness is at 2-150nm, and refractive index is 1.8-2.8, and conductivity is 10
-1-10
-8S/cm.
The crystallization rate of Si is at 50%-80% in the described multi-layer compound structure, and doping content is at 1%-5%, and thickness is at 2-30nm.
The conduction type of described conduction SiOx or SiCx is N-shaped, and its preparation adopts radio frequency plasma to strengthen chemical vapour deposition technique or hot-wire chemical gas-phase deposition technology or very high frequency plasma enhancing chemical vapour deposition technique or electron cyclotron resonance chemical vapor deposition technology or microwave plasma CVD technology.
Compared with prior art, the present invention has the following advantages:
Method of the present invention is by adopting a kind of advanced configuration to increase back reflection and reducing the light absorption of doped layer n layer and improve the silicon-base thin-film battery photoelectric conversion efficiency.When the preparation silicon-based thin film solar cell, in the n layer of the end battery of the p/i/n type silicon-based thin film solar cells of the n of unijunction layer or many knots, introduce nanometer silica or the silicon carbon film of conduction, form multi-layer compound film n layer, simultaneously Si and SiOx in the New n layer or SiCx doping, crystallization rate, thickness, refractive index, conductivity etc. are adjusted and optimized, increase back reflection and reduce the doped layer light absorption, improve the conversion efficiency of laminated cell.By above technological design, prepare the amorphous silicon of conversion efficiency more than 11.1%/nano-silicon dual stack battery and amorphous silicon/amorphous silicon germanium/nano-silicon three lamination batteries at large-sized substrate of the high deposition rate of 0.7nm/s and 0.8m2.
Description of drawings
By the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose of the present invention, Characteristics and advantages will be more clear.Identical Reference numeral may not be indicated identical part in whole accompanying drawings.Deliberately do not draw in proportion accompanying drawing, focus on illustrating purport of the present invention.In the accompanying drawings, for clarity sake, amplified the thickness of layer.
Fig. 1 is the flow chart of explanation the inventive method;
Fig. 2 is the structural representation of the three lamination silicon-based film solar cells of explanation the inventive method;
Fig. 3 is the structural representation of the three lamination silicon film solar batteries with MULTILAYER COMPOSITE N-shaped doped layer of explanation the inventive method;
Fig. 4 is the structural representation of the three lamination silicon film solar batteries with MULTILAYER COMPOSITE N-shaped doped layer of explanation the inventive method;
Fig. 5 is the structural representation of the three lamination silicon film solar batteries with MULTILAYER COMPOSITE N-shaped doped layer of explanation the inventive method.
Described diagram is illustrative, and nonrestrictive, can not excessively limit protection scope of the present invention at this.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization in the situation of intension of the present invention.Therefore the present invention is not subjected to the restriction of following public implementation.
The manufacture method of silicon-based thin-film lamination solar cell of the present invention is the N-shaped doped layer of multi-layer compound film N-shaped material as silicon-based thin film solar cell, is applicable to the n layer of end battery of the p/i/n type silicon-based thin film solar cells of the n layer of unijunction or many knots.The type of battery is for intrinsic i layer, namely comprise amorphous silica-based (amorphous silicon, amorphous silicon germanium, non-crystal silicon carbon or amorphous silica etc.), also comprise microcrystalline silicon (microcrystal silicon, crystallite SiGe, crystallite silicon-carbon or crystallite silica etc.), also comprise the thin film solar cell of nano silicon-based (microcrystal silicon, crystallite SiGe, crystallite silicon-carbon or crystallite silica etc.).This novel multi-layer laminated film N-shaped doped layer, its technology of preparing using plasma strengthens chemical vapour deposition technique or hot-wire chemical gas-phase deposition technology or electron cyclotron resonance chemical vapor deposition technology or microwave plasma CVD technology.
Fig. 1 is the flow chart of explanation the inventive method.The manufacture method of silicon-based thin-film lamination solar cell of the present invention comprises the following steps, at first deposit transparent conductive oxide film on transparency carrier; Then deposit successively anodal p1 layer, electric layer i1 and the negative pole n1 layer of the first battery on described transparent conductive oxide film surface; Perhaps continue anodal p2 layer, electric layer i 2 and negative pole n2 layer at surface deposition second battery of described the first battery, form the dual stack battery; Perhaps continue further to deposit at described the second battery surface anodal p3 layer, electric layer i3 and the negative pole n3 layer of the 3rd battery, form three lamination batteries.Wherein nanometer silica SiOx or the silicon-carbon SiCx film of in the nano-silicon n of crystallization layer, introducing conduction, the N-shaped doped layer of formation multi-layer compound film; At battery surface depositing electrically conductive thin film back electrode; Carry out at last laminating packaging and subsequent treatment.Described nano-silicon n layer comprises n1 layer or n3 layer, and it is the multi-layer compound structure of crystallization microcrystal silicon and crystallite silica.Multi-layer compound structure is SiOx/Si, or SiOx/Si/SiOx, or Si/SiOx/Si, or SiOx/Si/SiOx/Si, or SiOx/Si/SiOx/Si/SiOx, or SiCx/Si, or SiCx/Si/SiCx, or Si/SiCx/Si, or the SiCx/Si/SiCx/Si structure.SiOx or SiCx are the conductive layer of the crystallization of doping in the multi-layer compound structure, and crystallization rate is at 20-70%, and thickness is at 2-150nm, and refractive index is 1.8-2.8, and conductivity is 10
-1-10
-8S/cm.The crystallization rate of Si is at 50%-80% in the multi-layer compound structure, and doping content is at 1%-5%, and thickness is at 2-30nm.
The below is to prepare the preparation method of three lamination p/i/n type amorphous silicon film solar batteries NEW TYPE OF COMPOSITE plural layers N-shaped doped layer of the present invention as example illustrates.
With reference to testing: as shown in Figure 2, adopt chemical vapour deposition technique to prepare the SnO of 900nm at glass substrate 1
2: F film 2, as the front electrode of battery.Using plasma enhancing chemical vapour deposition technique deposits the amorphous silicon p1 layer 3 of 10nm, the amorphous silicon i1 layer 4 of 100nm, the amorphous silicon n1 layer 5 of 20nm successively on 2; Then continue the amorphous silicon p2 layer 6 of deposition 20nm; Continue to adopt silane, hydrogen and phosphine as reacting gas in nano- silicon n2 layer 8,8 deposition process of the amorphous silicon germanium i2 layer 7 of deposition 200nm and 20nm 6, wherein the ratio of phosphine and silane is 1.2%, and crystallization rate is 66%; Adopt silane, hydrogen and trimethyl borine as reacting gas in nano- silicon p3 layer 9,9 deposition process of then continuation deposition 20nm, the ratio of trimethyl borine and silane is 0.8%, and crystallization rate is 58%; Continue the nano-silicon i3 layer 10 of deposition 2000nm and the nano-silicon n3 layer 11 of 40nm 9.The Ag laminated film 12,12 of the ZnO:Al of sputter 60nm and 100nm is as the dorsum electrode layer of battery on 11; The battery for preparing carries out laminating packaging and forms encapsulated layer 13, and carries out reprocessing, and the conversion efficiency of the battery of three laminations of preparation is 9.7%.
Embodiment 1: as shown in Figure 3, adopt chemical vapour deposition technique to prepare the SnO of 900nm at glass substrate 1
2: F film 2, as the front electrode of battery.Using plasma enhancing chemical vapour deposition technique deposits the amorphous silicon p1 layer 3 of 10nm, the amorphous silicon i1 layer 4 of 100nm, the amorphous silicon n1 layer 5 of 20nm successively on 2; Then continue the amorphous silicon p2 layer 6 of deposition 20nm; Continue to adopt silane, hydrogen and phosphine as reacting gas in nano- silicon n2 layer 8,8 deposition process of the amorphous silicon germanium i2 layer 7 of deposition 200nm and 20nm 6, wherein the ratio of phosphine and silane is 1.2%, and crystallization rate is 66%; Adopt silane, hydrogen and trimethyl borine as reacting gas in nano- silicon p3 layer 9,9 deposition process of then continuation deposition 20nm, the ratio of trimethyl borine and silane is 0.8%, and crystallization rate is 58%; Nano-silicon i3 layer 10 at 9 continuation deposition 2000nm; Adopt silane, hydrogen and phosphine as reacting gas in nano- silicon n3 layer 11,11 deposition process of 2nm, wherein the ratio of phosphine and silane is 2.1%, and crystallization rate is 72%; The reacting gas of the SiOx layer 12,12 of 10nm is silane, hydrogen, phosphine and carbon dioxide, and crystallization rate is 30%, and refractive index is 2.0, and conductivity is 10
-6S/cm; Then deposit in nano- silicon n3 layer 13,13 deposition process of 4nm and adopt silane, hydrogen and phosphine as reacting gas, wherein the ratio of phosphine and silane is 2.1%, and crystallization rate is 72%; The Ag laminated film 14,14 of the ZnO:Al of sputter 60nm and 100nm is as the dorsum electrode layer of battery on 13; The battery for preparing carries out laminating packaging and forms encapsulated layer 15 and carry out reprocessing, and the conversion efficiency of the battery of three laminations of preparation is 10.5%.
Embodiment 2: as shown in Figure 4, adopt chemical vapour deposition technique to prepare the SnO of 900nm at glass substrate 1
2: F film 2, as the front electrode of battery.Using plasma enhancing chemical vapour deposition technique deposits the amorphous silicon p1 layer 3 of 10nm, the amorphous silicon i1 layer 4 of 100nm, the amorphous silicon n1 layer 5 of 20nm successively on 2; Then continue the amorphous silicon p2 layer 6 of deposition 20nm; Continue to adopt silane, hydrogen and phosphine as reacting gas in nano- silicon n2 layer 8,8 deposition process of the amorphous silicon germanium i2 layer 7 of deposition 200nm and 20nm 6, wherein the ratio of phosphine and silane is 1.2%, and crystallization rate is 66%; Adopt silane, hydrogen and trimethyl borine as reacting gas in nano- silicon p3 layer 9,9 deposition process of then continuation deposition 20nm, the ratio of trimethyl borine and silane is 0.8%, and crystallization rate is 58%; Nano-silicon i3 layer 10 at 9 continuation deposition 2000nm; Adopt silane, hydrogen and phosphine as reacting gas in nano- silicon n3 layer 11,11 deposition process of 3nm, wherein the ratio of phosphine and silane is 2.5%, and crystallization rate is 68%; The reacting gas of the SiOx layer 12,12 of 10nm is silane, hydrogen, phosphine and carbon dioxide, and crystallization rate is 40%; Refractive index is 2.4, and conductivity is 10
-5S/cm; Then deposit in nano- silicon n3 layer 13,13 deposition process of 5nm and adopt silane, hydrogen and phosphine as reacting gas, wherein the ratio of phosphine and silane is 2.5%, and crystallization rate is 68%; The Ag laminated film 14,14 of the ZnO:Al of sputter 60nm and 100nm is as the dorsum electrode layer of battery on 13; The battery for preparing carries out laminating packaging and forms encapsulated layer 15 and carry out reprocessing, and the conversion efficiency of the battery of three laminations of preparation is 11.1%.
Embodiment 3: as shown in Figure 5, adopt chemical vapour deposition technique to prepare the SnO of 900nm at glass substrate 1
2: F film 2, as the front electrode of battery.Using plasma enhancing chemical vapour deposition technique deposits the amorphous silicon p1 layer 3 of 10nm, the amorphous silicon i1 layer 4 of 100nm, the amorphous silicon n1 layer 5 of 20nm successively on 2; Then continue the amorphous silicon p2 layer 6 of deposition 20nm; Continue to adopt silane, hydrogen and phosphine as reacting gas in nano- silicon n2 layer 8,8 deposition process of the amorphous silicon germanium i2 layer 7 of deposition 200nm and 20nm 6, wherein the ratio of phosphine and silane is 1.2%, and crystallization rate is 66%; Adopt silane, hydrogen and trimethyl borine as reacting gas in nano- silicon p3 layer 9,9 deposition process of then continuation deposition 20nm, the ratio of trimethyl borine and silane is 0.8%, and crystallization rate is 58%; Nano-silicon i3 layer 10 at 9 continuation deposition 2000nm; The reacting gas of the SiC layer 11,11 of 8nm is silane, hydrogen, phosphine and methane, and crystallization rate is 30%, and refractive index is 2.1, and conductivity is 10
-5S/cm; Then deposit in nano- silicon n3 layer 12,12 deposition process of 6nm and adopt silane, hydrogen and phosphine as reacting gas, wherein the ratio of phosphine and silane is 2.5%, and crystallization rate is 68%; The Ag laminated film 14,14 of the ZnO:Al of sputter 60nm and 100nm is as the dorsum electrode layer of battery on 13; The battery for preparing carries out laminating packaging and forms encapsulated layer 15 and carry out reprocessing, and the conversion efficiency of the battery of three laminations of preparation is 10.2%.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction.Any those of ordinary skill in the art are not breaking away from the technical solution of the present invention scope situation, all can utilize the technology contents of above-mentioned announcement that technical solution of the present invention is made many possible changes and modification, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not break away from technical solution of the present invention, all still belongs in the protection range of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment does according to technical spirit of the present invention.
Claims (7)
1. the manufacture method of a silicon-based thin-film lamination solar cell comprises:
Deposit transparent conductive oxide film on transparency carrier;
Deposit successively anodal p1 layer, electric layer i1 and the negative pole n1 layer of the first battery on described transparent conductive oxide film surface; And/or
At anodal p2 layer, electric layer i2 and the negative pole n2 layer of surface deposition second battery of described the first battery, form the dual stack battery; And/or
Anodal p3 layer, electric layer i3 and negative pole n3 layer at the further deposition of described the second battery surface the 3rd battery form three lamination batteries;
Wherein,
In the nano-silicon n of crystallization layer, introduce nanometer silica SiOx or the silicon-carbon SiCx film of conduction, form the N-shaped doped layer of multi-layer compound film;
At battery surface depositing electrically conductive thin film back electrode;
Carry out laminating packaging and subsequent treatment.
2. method according to claim 1, it is characterized in that: described nano-silicon n layer comprises n1 layer or n2 layer or n3 layer.
3. method according to claim 2, it is characterized in that: described nano-silicon n layer is the multi-layer compound structure of crystallization microcrystal silicon and crystallite silica.
4. method according to claim 3, it is characterized in that: multi-layer compound structure is SiOx/Si, or SiOx/Si/SiOx, or Si/SiOx/Si, or SiOx/Si/SiOx/Si, or SiOx/Si/SiOx/Si/SiOx, or SiCx/Si, or SiCx/Si/SiCx, or Si/SiCx/Si, or the SiCx/Si/SiCx/Si structure.
5. method according to claim 4 is characterized in that: SiOx or SiCx are the conductive layer of the crystallization that mixes in the described multi-layer compound structure, and crystallization rate is at 20-70%, and thickness is at 2-150nm, and refractive index is 1.8-2.8, and conductivity is 10
-1-10
-8S/cm.
6. method according to claim 4, it is characterized in that: the crystallization rate of Si is at 50%-80% in the described multi-layer compound structure, and doping content is at 1%-5%, and thickness is at 2-30nm.
7. method according to claim 1, it is characterized in that: the conduction type of described conduction SiOx or SiCx is N-shaped, and its preparation adopts radio frequency plasma to strengthen chemical vapour deposition technique or hot-wire chemical gas-phase deposition technology or very high frequency plasma enhancing chemical vapour deposition technique or electron cyclotron resonance chemical vapor deposition technology or microwave plasma CVD technology.
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| CN103618024A (en) * | 2013-10-21 | 2014-03-05 | 福建铂阳精工设备有限公司 | Method of improving photoelectric conversion efficiency of microcrystalline silicon thin film solar cell |
| CN104319306A (en) * | 2014-11-03 | 2015-01-28 | 云南师范大学 | Efficient laminated thin film solar cell and preparing method thereof |
| CN109390430A (en) * | 2018-10-19 | 2019-02-26 | 君泰创新（北京）科技有限公司 | A kind of lamination solar cell and preparation method thereof |
| CN113921661A (en) * | 2021-09-23 | 2022-01-11 | 上海理想万里晖薄膜设备有限公司 | Method for producing a heterojunction solar cell and heterojunction solar cell |
| CN117038754A (en) * | 2023-10-08 | 2023-11-10 | 长三角物理研究中心有限公司 | Flexible thin film silicon-based solar cell and preparation method thereof |
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| CN117038754B (en) * | 2023-10-08 | 2024-01-26 | 长三角物理研究中心有限公司 | Flexible thin film silicon-based solar cell and preparation method thereof |
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