CN102891191A - Amorphous silicon intermediate zone solar battery and preparation method thereof - Google Patents

Amorphous silicon intermediate zone solar battery and preparation method thereof Download PDF

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Publication number
CN102891191A
CN102891191A CN2012103758727A CN201210375872A CN102891191A CN 102891191 A CN102891191 A CN 102891191A CN 2012103758727 A CN2012103758727 A CN 2012103758727A CN 201210375872 A CN201210375872 A CN 201210375872A CN 102891191 A CN102891191 A CN 102891191A
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amorphous silicon
intermediate gray
silicon intermediate
wire
solar cell
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CN2012103758727A
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周天微
曹权
左玉华
王启明
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Institute of Semiconductors of CAS
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Institute of Semiconductors of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides an amorphous silicon intermediate zone solar battery and a preparation method thereof. The amorphous silicon intermediate zone battery comprises a conductive substrate, an n-type nanowire, an amorphous silicon intermediate zone layer, a p-type amorphous silicon layer and a transparent conductive film layer, wherein the n-type nanowire is formed on the conductive substrate; the amorphous silicon intermediate zone layer is formed on the n-type nanowire; the p-type amorphous silicon layer is formed on the amorphous silicon intermediate zone layer; and the transparent conductive film layer is formed on the p-type amorphous silicon layer. According to the invention, through utilizing the characteristics of high orientation, duty ratio and controllable specific surface of the nanowire material, a rapid channel is provided for a photon-generated carrier, combination is reduced, and the collecting efficiency of the photon-generated carrier is improved.

Description

Amorphous silicon Intermediate Gray solar cell and preparation method thereof
Technical field
The present invention relates to the photovoltaic technical field of new energies, especially relate to a kind of amorphous silicon Intermediate Gray solar cell and preparation method thereof.
Background technology
When the non-renewable energy resources such as electric power, coal, oil signal for help repeatedly, energy problem is day by day serious.Solar energy power generating becomes the focus of people's research as one of most promising new forms of energy.Silica-based solar cell since aboundresources, developing history early and the technology comparative maturity, maintain the leading position, but because the restriction of material and technique is difficult to reduce cost always.And amorphous silicon absorbs far above crystalline silicon in the light absorption of visible range, so battery can be very thin, and the preparation method of amorphous silicon battery is simple, cost is low, thereby becomes one of research topic that present people pay close attention to.
Amorphous silicon film battery has seriously hindered the Industry Promotion application because conversion efficiency is low.And the key factor that restriction efficient improves is that reflection loss is high, surface recombination is large, collection efficiency low and long-wave response is poor.In order to retrieve the long wave loss, utilize the impurity engineering, forming the deep energy level Intermediate Gray in the amorphous silicon forbidden band is an important optimization approach breaking through the infrared band response.The introducing of Intermediate Gray with visible and infrared compatible one, can effectively utilize original lower energy photon that does not utilize, the output of increase short circuit current.Guaranteeing to increase the conversion efficiency of battery under the constant prerequisite of open circuit voltage.
Although the amorphous silicon Intermediate Gray can be increased in the spectral absorption of long wave band, the preparation of amorphous silicon Intermediate Gray still has a lot of difficulties.Especially because the strong scattering that heavy doping causes and magnetic tape trailer attitude, the dangling bonds of amorphous silicon itself affect the mobility of charge carrier and effectively collect transportation, cause the photo-generated carrier collection efficiency low.
Summary of the invention
The technical problem that (one) will solve
In view of this, the invention provides a kind of amorphous silicon Intermediate Gray solar cell and preparation method thereof for preparing, to improve the collection efficiency of photo-generated carrier.
(2) technical scheme
According to an aspect of the present invention, provide a kind of amorphous silicon Intermediate Gray solar cell, having comprised: conductive substrates; The N-shaped nano wire is formed on the conductive substrates; Belt in the middle of the amorphous silicon is formed on the N-shaped nano wire; The p-type amorphous silicon layer is formed on the middle belt of amorphous silicon; The transparent conductive film layer is formed on the p-type amorphous silicon layer.
According to another aspect of the present invention, also provide a kind of preparation method of amorphous silicon Intermediate Gray solar cell, having comprised: prepare nano wire in conductive substrates; Nano wire mixed form the N-shaped nano wire; At N-shaped nano wire growth amorphous silicon Intermediate Gray intrinsic material; Growing p-type amorphous silicon layer on amorphous silicon Intermediate Gray intrinsic material; Prepare the transparent conductive film layer at the p-type amorphous silicon layer, thereby finish the preparation of amorphous silicon Intermediate Gray solar cell.
(3) beneficial effect
Can find out that from technique scheme the present invention prepares amorphous silicon Intermediate Gray solar cell and preparation method thereof and has following beneficial effect:
(1) nano-material has height-oriented property, duty ratio and the controlled characteristic of specific surface, thereby for photo-generated carrier provides quick passage, reduces compoundly, has improved the collection efficiency of photo-generated carrier;
(2) absorption region of spectrum can be effectively expanded in the introducing of transition metal impurity in the intermediate zone material, improves long wave and absorbs, thereby improved battery conversion efficiency.
Description of drawings
Fig. 1 is the generalized section according to the amorphous silicon Intermediate Gray solar cell of the embodiment of the invention;
Fig. 2 is the flow chart according to the preparation amorphous silicon Intermediate Gray solar cell method of the embodiment of the invention;
Fig. 3 is that embodiment of the invention amorphous silicon Intermediate Gray solar cell and common amorphous silicon p-i-n structure solar cell are at the absorption spectra comparison diagram of near infrared band.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.Need to prove that in accompanying drawing or specification description, similar or identical part is all used identical figure number.The implementation that does not illustrate in the accompanying drawing or describe is form known to a person of ordinary skill in the art in the affiliated technical field.
In addition, although this paper can provide the demonstration of the parameter that comprises particular value, should be appreciated that parameter need not definitely to equal corresponding value, but can in acceptable error margin or design constraint, be similar to corresponding value.
Technical scheme of the present invention is to utilize electrochemical process or hydro thermal method to prepare nano wire at substrate.Nano wire is put into the material growing devices such as magnetron sputtering or PECVD, growth intrinsic amorphous silicon, amorphous silicon intermediate zone material, P type amorphous silicon, form ZnO nano-wire/i type intrinsic amorphous silicon intermediate zone material/p-type amorphous silicon structures, be called for short: n-i (IB)-p radial structure.Wherein, i represents i layer intrinsic amorphous silicon, and IB represents Intermediate Gray.Deposit at last the ITO layer, form the amorphous silicon Intermediate Gray solar cell of nanometer radial structure.
In one exemplary embodiment of the present invention, provide a kind of amorphous silicon Intermediate Gray solar cell.As shown in Figure 1, this amorphous silicon Intermediate Gray solar cell comprises: conductive substrates, and be formed at successively top layer belt, p-type amorphous silicon layer and transparent conductive film layer in the middle of the N-shaped ZnO nano-wire of transpassivation, amorphous silicon on this conductive substrates.
In the present embodiment, at the bottom of the substrate of employing can be stainless steel lining, also can be Conducting Glass.Those skilled in the art also can adopt the substrate of other types as required.
In the above-mentioned N-shaped ZnO nano-wire, according to the common way of semiconductor applications, it is the ZnO nano-wire of producing to be carried out the nitrogen phosphorus doping form.In addition, because the specific area of N-shaped ZnO nano-wire is large, surface state is many, so in the lower intrinsic amorphous silicon layer of surface sputtering growth one deck defect state, surface state that can the passivation nano wire.
Although it will be apparent to those skilled in the art that the ZnO nano-wire that present embodiment adopts, also can adopt the nano wire of other types, such as Si nano wire, C nano wire etc.
In the present embodiment because nano wire has height-oriented property, duty ratio and the controlled characteristic of specific surface, thereby for photo-generated carrier provides quick passage, reduces compound, the collection efficiency of raising photo-generated carrier.
Belt is the heavily doped amorphous silicon Intermediate Gray of transition metal intrinsic material in the middle of the above-mentioned amorphous silicon.Wherein, transition metal refers to introduce the metal of deep energy level in the forbidden band, as: the elements such as titanium, chromium, cobalt.Heavy doping is that doping content is greater than 5 * 10 19Cm -3Above doping.Take transition metal impurity as example as titanium elements, the doping content of Ti is 10 20Cm -3More than.
In the present embodiment, the absorption region of spectrum can be effectively expanded in the introducing of transition metal impurity in the intermediate zone material, improves long wave and absorbs, thereby improved battery conversion efficiency.
In the present embodiment, belt and p-type amorphous silicon layer consist of n-i (IB)-p radial structure in the middle of N-shaped ZnO nano-wire, the amorphous silicon, this radial nanowire separates the direction of light absorption and the refined cloud collection of charge carrier, utilize nanowire length direction absorption optical, utilize nano wire radially to collect photo-generated carrier.Because nanowire length is much larger than its radius, the photo-generated carrier that light fully absorbs generation is collected in short distance, reduces compound in transporting of photo-generated carrier.
Fig. 2 is the flow chart according to embodiment of the invention amorphous silicon Intermediate Gray preparation method of solar battery.Please refer to Fig. 1 and Fig. 2, this method for preparing amorphous silicon Intermediate Gray solar cell comprises:
Steps A, making ZnO nano wire on conductive substrates;
The method of making ZnO nano wire is generally chemical synthesis process, as: electrochemical process, solution chemistry growth method or hydro thermal method.Utilize the ZnO nano-wire of chemical synthesis process preparation, cost is low and realize easily the large tracts of land industrialization.
Take the electrochemical production ZnO nano-wire as example, the kind of concentration, solvent and solute by adjusting operating voltage and electric current, electrolyte solution can be prepared ordering, the controlled zinc oxide nanowire of length, and the about 1 μ m of length is about diameter 100nm.
Step B carries out nitrogen phosphorus gas phase doping to this ZnO nano-wire and forms the N-shaped ZnO nano-wire;
Step C at the superficial deposit intrinsic amorphous silicon of ZnO nano-wire, carries out passivation to the surface state of this N-shaped ZnO nano-wire;
In this step, by adjusting the flow-rate ratio of argon gas and hydrogen, utilize the grow intrinsic amorphous silicon of some nm of magnetically controlled sputter method.
Step D, the flow-rate ratio of adjustment argon gas and hydrogen, the amorphous silicon Intermediate Gray intrinsic material that the magnetic control co-sputtering transition metal impurity mixes on above-mentioned ZnO nano-wire, the about 400nm of thickness of this amorphous silicon Intermediate Gray intrinsic material.
Step e, growing p-type amorphous silicon layer on amorphous silicon Intermediate Gray intrinsic material forms the n-i-p radial structure;
The method of growing P-type amorphous silicon layer is generally the PECVD method, control structure and the performance of P type amorphous silicon layer by adjusting silane and the flow-rate ratio of hydrogen, flow, radio-frequency power and the depositing temperature etc. of borine, about tens nm of thickness form n-i (IB)-p radial structure.
Step F, the p-type amorphous silicon layer prepare transparent conductive film (be called for short: ITO) layer, thereby finish the preparation of amorphous silicon Intermediate Gray solar cell.
In this step, the method for preparing transparent conductive film can be the methods such as thermal evaporation, magnetron sputtering, or chemical vapour deposition (CVD).To adopt thermal evaporation method as example, under appropriate oxygen partial pressure, evaporate In 2O 3And SnO 2Mixture can obtain transparent conductive film (ITO), the about 40nm of thickness.
Fig. 3 is that embodiment of the invention amorphous silicon Intermediate Gray solar cell and common amorphous silicon p-i-n structure solar cell are at the absorption spectra comparison diagram of near infrared band.Wherein, round dot is amorphous silicon Intermediate Gray battery of the present invention, and side's point is common amorphous silicon p-i-n structure solar cell.Fig. 3 as can be known, the infrared band that is absorbed in of the more common amorphous silicon battery of amorphous silicon Intermediate Gray solar cell of the present invention is significantly improved.
Among the present invention, with ZnO radial nanowire and the amorphous silicon intermediate zone material solar cell in conjunction with preparation, not only expand the absorption of long wave spectrum, and solved the efficient problem that falls into light and efficient carrier collection.This is a kind of very promising solar cell.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (12)

1. an amorphous silicon Intermediate Gray solar cell is characterized in that, comprising:
Conductive substrates;
The N-shaped nano wire is formed on the described conductive substrates;
Belt in the middle of the amorphous silicon is formed on the described N-shaped nano wire;
The p-type amorphous silicon layer is formed on the middle belt of described amorphous silicon;
The transparent conductive film layer is formed on the described p-type amorphous silicon layer.
2. amorphous silicon Intermediate Gray solar cell according to claim 1 is characterized in that, described N-shaped nano wire is the ZnO nano-wire of nitrogen phosphorus doping.
3. amorphous silicon Intermediate Gray solar cell according to claim 2 is characterized in that, also comprises: intrinsic amorphous silicon, be deposited on described N-shaped ZnO nano-wire top layer, and be used for its surface state of passivation.
4. amorphous silicon Intermediate Gray solar cell according to claim 1 is characterized in that, belt is the heavily doped amorphous silicon Intermediate Gray of transition metal intrinsic material in the middle of the described amorphous silicon.
5. amorphous silicon Intermediate Gray solar cell according to claim 4 is characterized in that, described transition metal is titanium, chromium or cobalt; Described heavily doped doping content is greater than 5 * 10 19Cm -3
6. amorphous silicon Intermediate Gray solar cell according to claim 5 is characterized in that, described transition metal is titanium, and described doping content is greater than 10 20Cm -3
7. each described amorphous silicon Intermediate Gray solar cell in 6 according to claim 1 is characterized in that, described substrate is at the bottom of the stainless steel lining or Conducting Glass.
8. the preparation method of an amorphous silicon Intermediate Gray solar cell is characterized in that, comprising:
Prepare nano wire in conductive substrates;
Described nano wire mixed form the N-shaped nano wire;
At described N-shaped nano wire growth amorphous silicon Intermediate Gray intrinsic material;
Growing p-type amorphous silicon layer on described amorphous silicon Intermediate Gray intrinsic material;
Prepare the transparent conductive film layer at described p-type amorphous silicon layer, thereby finish the preparation of amorphous silicon Intermediate Gray solar cell.
9. amorphous silicon Intermediate Gray preparation method of solar battery according to claim 8 is characterized in that, described nano wire is ZnO nano-wire;
Described the nano wire step that forms the N-shaped nano wire of mixing is comprised: described ZnO nano-wire is carried out the nitrogen phosphorus doping to form the N-shaped ZnO nano-wire.
10. amorphous silicon Intermediate Gray preparation method of solar battery according to claim 9 is characterized in that, describedly also comprises before the step of N-shaped nano wire growth amorphous silicon Intermediate Gray intrinsic material:
Superficial deposit intrinsic amorphous silicon at described N-shaped ZnO nano-wire carries out passivation to its surface state.
11. amorphous silicon Intermediate Gray preparation method of solar battery according to claim 8, it is characterized in that described step at ZnO nano-wire growth amorphous silicon Intermediate Gray intrinsic material comprises: at the amorphous silicon Intermediate Gray intrinsic material of described ZnO nano-wire growth transition metal impurity doping.
12. amorphous silicon Intermediate Gray preparation method of solar battery according to claim 11 is characterized in that described transition metal is titanium, chromium or cobalt; Described heavily doped doping content is greater than 5 * 10 19Cm -3
CN2012103758727A 2012-09-29 2012-09-29 Amorphous silicon intermediate zone solar battery and preparation method thereof Pending CN102891191A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106206779A (en) * 2016-08-01 2016-12-07 中国科学院高能物理研究所 Heterojunction solar battery with silicon nano column array as substrate and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080135089A1 (en) * 2006-11-15 2008-06-12 General Electric Company Graded hybrid amorphous silicon nanowire solar cells
US20090289320A1 (en) * 2008-05-21 2009-11-26 International Business Machines Corporation Fast p-i-n photodetector with high responsitivity
CN102544243A (en) * 2012-03-29 2012-07-04 中国科学院半导体研究所 Intermediate zone material of amorphous silicon film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080135089A1 (en) * 2006-11-15 2008-06-12 General Electric Company Graded hybrid amorphous silicon nanowire solar cells
US20090289320A1 (en) * 2008-05-21 2009-11-26 International Business Machines Corporation Fast p-i-n photodetector with high responsitivity
CN102544243A (en) * 2012-03-29 2012-07-04 中国科学院半导体研究所 Intermediate zone material of amorphous silicon film and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106206779A (en) * 2016-08-01 2016-12-07 中国科学院高能物理研究所 Heterojunction solar battery with silicon nano column array as substrate and preparation method thereof

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Application publication date: 20130123