CN105514182A - Method, material and application for solar energy battery surface passivation and current collection - Google Patents

Method, material and application for solar energy battery surface passivation and current collection Download PDF

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Publication number
CN105514182A
CN105514182A CN201610081430.XA CN201610081430A CN105514182A CN 105514182 A CN105514182 A CN 105514182A CN 201610081430 A CN201610081430 A CN 201610081430A CN 105514182 A CN105514182 A CN 105514182A
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Prior art keywords
conductive film
transparent
nano
stack
layer
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李翔
黎微明
潘景伟
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Jiangsu Weidao Nano Equipment Technology Co Ltd
Wuxi Lead Intelligent Equipment Co Ltd
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Jiangsu Weidao Nano Equipment Technology Co Ltd
Wuxi Lead Intelligent Equipment Co Ltd
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Priority to CN201610081430.XA priority Critical patent/CN105514182A/en
Publication of CN105514182A publication Critical patent/CN105514182A/en
Priority to CN201710063481.4A priority patent/CN106981539A/en
Priority to PCT/CN2018/074886 priority patent/WO2018141249A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C—CHEMISTRY; METALLURGY
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
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    • H01L31/02—Details
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Abstract

The invention belongs to the field of semiconductor devices, and particularly relates to the field of solar battery manufacturing. On the basis of technological processes of the existing PERC battery technology, a metallic oxide nanometer laminated conductive film prepared through the atomic layer deposition technology is used as a passivation layer, so that the problem that parasitic resistance and contact resistance are large is solved, the battery conversion efficiency is improved, and the mass production is achieved.

Description

For the method for solar cell surface passivation and electric current collection, material and application
Technical field
This patent belongs to field of semiconductor devices, is specifically related to solar cell and manufactures field, particularly relates to the transparency electrode prepared in conjunction with technique for atomic layer deposition for the method for the passivation of solar cell surface and electric current collection, material and application.
Background technology
Surface passivation is the important technical reducing surface recombination rate, improve the conversion efficiency of silicon solar cell.(SolarEnergyMaterials & SolarCells, 2006, (90): 82-92) passivation emitter rear-face contact technology (PERC technology), backside passivation layer is done, collocation silicon nitride film anti-reflection layer with the method plating alundum (Al2O3) film of PECVD after surperficial flocking and diffusion.Because alundum (Al2O3) and silicon nitride are insulating material, follow-up silver slurry aluminium paste electrode will to be done with silicon face by the method for laser drilling and be connected.But the area of laser beam drilling is limited, so the dead resistance of electrode and silicon and contact resistance can have influence on the collection of electric current thus affect the efficiency of battery, and partially perforation causes the complex process of PERC technology, and partially perforation also can cause tapping to there is compound phenomenon.Germany's Fraunhofer solar energy research institute (FraunhoferISE) devises contact passivating technique: passivation layer is the passivation that the ultra-thin silica of one deck and one deck doped silicon thin layer are formed, without the need to perforate, the conduction of passivation layer is realized by metal oxide tunneling effect, but passivation layer itself is very thin, the technique relative complex of needs.Therefore, on the basis of PERC technology, also need to develop the surface passivation method without the need to partially perforation.
Another kind of scheme is, adopts conductive material as passivation layer to replace alundum (Al2O3), is expected to solve dead resistance and the large problem of contact resistance, promotes battery conversion efficiency.Transparent conductive oxide (TCO) is widely applied at field of photoelectric devices as electrode material, wherein zinc oxide (the AluminumdopedZincoxide of aluminium doping, AZO) there is the features such as simple, the easy realization doping of preparation technology, there is document (SolarEnergy, 2014 (110), 595 – 602) report, by the AZO of wet-layer preparation, there is certain passivation properties, but the technique of wet-layer preparation is comparatively complicated, is not suitable for large-scale production.Technique for atomic layer deposition (ALD technology) is the film growth techniques of a kind of advanced person.Adopt that ALD technology processability is excellent, there is not been reported for the transparent conductive oxide material that is adapted at doing in PERC technology passivation layer.
Summary of the invention
1, technical problem to be solved by this invention
The present invention be directed to the technological process of existing PERC battery technology, adopt ALD technology to process, directly with can conductive transparent material layer as passivation layer, thus solution dead resistance and the large problem of contact resistance, promote battery conversion efficiency, and be applicable to produce in enormous quantities.
2, technical scheme provided by the invention
The conductive film that the nano-stack prepared based on technique for atomic layer deposition (ALD) is transparent, for passivation and the electric current collection of solar cell surface.Concrete technical scheme is as follows:
The preparation method of the conductive film that nano-stack is transparent, adopts technique for atomic layer deposition to be prepared, specifically comprises step main as follows:
(1) by go to carry on the back close washed after silicon cell be loaded into the cavity of plated film, need the face of plated film in cavity in exposed state, do not need the face of plated film to block;
(2) cavity vacuumizes and keeps the technique vacuum in cavity constant, heats the technological temperature making the temperature in cavity reach required;
(3) circulate 10 Al 2o 3deposition as transition zone;
(4) deposition of circulation n1 ZnO, circulation n2 Al 2o 3deposition;
(5) technique in repetition step (4) n3 time, until prepare required nano-stack conductive film;
(6) cavity is directly lowered the temperature or is lowered the temperature after increasing annealing steps, and vacuum breaker takes out silicon cell.
Particularly, in step (1), added to multi-disc silicon cell man-hour: when cell backside plated film, put face-to-face by multi-disc battery and compress, when battery front side plated film, put back-to-back for two panels battery and compress, to save the space of process chamber, increasing production capacity.
Particularly, the range of choice of the technique vacuum in step (2) be 100 handkerchiefs to 1000 handkerchiefs, the range of choice of technological temperature is 100-300 degree Celsius.
Particularly, step (3) is passed through completely independently pipeline in cavity, is carried the steam of trimethyl aluminium and deionized water in a pulsed fashion, and carrier gas adopts nitrogen; The pulse train of each deposition cycle is: trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purge, and the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
Particularly, step (4) is passed through completely independently pipeline and in cavity, is carried diethyl zinc in a pulsed fashion, the steam of trimethyl aluminium and deionized water, and carrier gas adopts nitrogen; The pulse train of each deposition cycle of ZnO is: diethyl zinc pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purge, and the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds; Al 2o 3the pulse train of each deposition cycle is: trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purge, and the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
Particularly, the frequency n 1 of circulation, n2, n3 collocation need the aluminium oxide that the reaches doping level in the transparent conductive film of described nano-stack to be as the criterion with practical application; Wherein, the scope of the scope of the frequency n 1 of circulation to be the scope of 1-100, n2 be 1-10, n3 is 1-1000.
Particularly, in step (6), after being circulated throughout of deposition plating, also can increase the step of annealing before cavity cooling, the annealing temperature that required annealing time needs with practical application is as the criterion.Such as the annealing temperature of 500 degrees Celsius adopts the annealing of 30 minutes.
Conductive film transparent for nano-stack is used for the application of the passivation layer in solar cell, the conductive film that nano-stack is transparent adopts said method preparation, the conductive film that nano-stack is transparent when n-type is adulterated can be used for the field passivation of cell p emitter, and the conductive film that nano-stack is transparent when p-type adulterates is used for the field passivation of battery n emitter.
Particularly, the conductive film that described nano-stack is transparent mainly comprises by ZnO layer and Al 2o 3the elementary cell of layer composition; The cycle-index of elementary cell itself is n3; In elementary cell, in ZnO layer, the cycle-index of ZnO individual layer is n1, Al 2o 3al in layer 2o 3the cycle-index of individual layer is n2; The gross thickness of film is n3 × (thickness × n1+Al of ZnO individual layer 2o 3thickness × the n2 of individual layer); The doping level of aluminium oxide in the transparent conductive film of described nano-stack is n2/ (n1+n2) at%; Wherein, the frequency n 1 of circulation and the scope of n2 are the scope of 1-100 and 1-10, n3 is respectively 1-1000.
Particularly, the scope of the gross thickness of the conductive film that nano-stack is transparent is between 5 nanometers to 200 nanometers.
More specifically, technique vacuum 100 handkerchief when preparing film in step (2), technological temperature are 200 degrees Celsius, the thickness of ZnO individual layer is 0.12nm, error range ± 0.01nm (can be different with instrument error scope according to different method of testings, in the acceptable error range of those skilled in the art, lower same), Al 2o 3the thickness of individual layer is 0.1nm, error range ± 0.01nm; With this understanding, when the aluminium doping level of the transparent conductive film of nano-stack (comprises endpoint value herein) between 1.0at% to 7.1at%, the resistivity of film is 1.5 × 10 -3ohmcm is to 3.0 × 10 -3(endpoint value is comprised herein) between ohmcm.
By the conductive film back of the body passivation layer be used in the solar cell of PERC structure transparent for the nano-stack adopting said method to prepare, be used in p+ emitter type n semiconductor material and do a passivation, or do a passivation at n+ emitter p-type semi-conducting material.Passivation effect than traditional aluminium back surface field battery (as SolarEnergy, 2014 (110), 595 – 602) in photoelectric conversion efficiency, at least can promote 0.8%, electric conductivity can accomplish that the aluminium back surface field battery directly contacted with sial is suitable.
About other operable materials, for AZO, the material of ZnO doping three races is as B, Al, Ga, In; Or seven races' material such as Cl, I can become type n semiconductor material.The material of ZnO doping first family is as Li, Na, K; Or the 5th race's material such as N, P, As can become p-type semi-conducting material.
3, beneficial effect:
(1) back of the body passivation layer of conductive film in the solar cell for PERC structure that the nano-stack prepared of this patent is transparent, passivation effect at least can promote 0.8% than traditional aluminium back surface field battery in photoelectric conversion efficiency, and electric conductivity can accomplish that the aluminium back surface field battery directly contacted with sial is suitable.
(2) Al of PERC battery 2o 3passivation is based on Al 2o 3inner with field, the interface passivation effect that reaches of negative electrical charge.ZnO is n-type semiconductor inherently, more free electron can be provided to reach the effect reducing its resistivity by Al doping.
(3) adopt transparent conductive oxide as passivation layer, can not shut out the light and reduce the conversion efficiency of solar cell.
Accompanying drawing explanation
The cyclic sequence of the conductive film that Fig. 1 nano-stack is transparent
The conductive film that Fig. 2 nano-stack is transparent is used in an example of the passivation application on p-type PERC battery.
The conductive film that Fig. 3 nano-stack is transparent is used in an example of the passivation application on n-type battery.
Embodiment
Below in conjunction with Figure of description and specific embodiment, the present invention is described in detail.
Embodiment 1
Adopt in this patent different process conditions (technique vacuum, technological temperature), different proportionings (numerical value of n1, n2, n3, the doping level (n2/ (n1+n2) at%) of aluminium oxide, prepare the film of heterogeneity (thickness, resistivity), the relation of concrete each parameter is as follows:
Table 1 preparation condition, the table of comparisons between composition and character
Embodiment 2
In order to realize object of the present invention, the lower material of resistivity is adopted to be more convenient for collected current, consider the factor such as preparation condition, proportioning, under the condition of technique vacuum 100 handkerchief, technological temperature 200 degrees Celsius, fixing n2=1, when controlled oxidization aluminium doping level is in the film between 1at% to 7at%, the resistivity of film is less, 1.5 × 10 -3ohmcm is to 3.0 × 10 -3change between ohmcm, and with 1.5 × 10 in test -3ohmcm is a minimum measured value.
The preparation condition of table 1 preferred embodiment, the table of comparisons between composition and character
Embodiment 3
Conductive film transparent for the nano-stack adopting this patent method to prepare is used for the emitter passivation in the solar cell of PERC structure.With reference to shown in Fig. 2, replace the alumina layer in PERC battery with the zinc-oxide film of aluminium doping, its p emitter of electronegative meeting to the back side play the effect of passivation.Meanwhile, this conductive film can play the effect of collected current, reduces the contact resistance raised because perforated area is little.The upper surface of this battery also can do passivation with the transparent conductive film of p-type doping.
Embodiment 4
Conductive film transparent for the transparent nano-stack adopting this patent method to prepare is used for the emitter passivation in n-type crystal silicon solar batteries.With reference to shown in Fig. 3, the zinc-oxide film adulterated with aluminium is to the passivation of battery upper surface p emitter.Meanwhile, this conductive film can play the effect of collected current, and this film is less in the absorption of visible frequency, can not affect light through.Passivation also can be done with the transparent conductive film of p-type doping in the back side of this battery.
Below be schematically described creation of the present invention and execution mode thereof, protection scope of the present invention includes but not limited to above-mentioned description.One of execution mode of the also just the invention shown in accompanying drawing, actual structure is not limited thereto.So; if those of ordinary skill in the art is subject to enlightenment of the present invention; when not departing from creation aim of the present invention, designing the frame mode similar to technical scheme of the present invention and embodiment without creationary, the protection range of this patent all should be belonged to.

Claims (11)

1. a preparation method for the conductive film that nano-stack is transparent, is characterized in that: adopt technique for atomic layer deposition to be prepared, specifically comprise step main as follows:
(1) by go to carry on the back close washed after silicon cell be loaded into the cavity of plated film, need the face of plated film in cavity in exposed state, do not need the face of plated film to block;
(2) cavity vacuumizes and keeps the technique vacuum in cavity constant, heats the technological temperature making the temperature in cavity reach required;
(3) circulate 10 Al 2o 3deposition as transition zone;
(4) deposition of circulation n1 ZnO, circulation n2 Al 2o 3deposition;
(5) technique in repetition step (4) n3 time, until prepare required nano-stack conductive film;
(6) cavity is directly lowered the temperature or is lowered the temperature after increasing annealing steps, and vacuum breaker takes out silicon cell.
2. the preparation method of the conductive film that a kind of nano-stack according to claim 1 is transparent, it is characterized in that: in step (1), added to multi-disc silicon cell man-hour: when cell backside plated film, multi-disc battery is put face-to-face and compresses, when battery front side plated film, put back-to-back for two panels battery and compress, to save the space of process chamber, increase production capacity.
3. the preparation method of the conductive film that a kind of nano-stack according to claim 1 and 2 is transparent, it is characterized in that: the range of choice of the technique vacuum in step (2) be 100 handkerchiefs to 1000 handkerchiefs, the range of choice of technological temperature is 100-300 degree Celsius.
4. the preparation method of the conductive film that a kind of nano-stack according to claim 3 is transparent, it is characterized in that: step (3) is passed through completely independently pipeline in cavity, carried the steam of trimethyl aluminium and deionized water in a pulsed fashion, and carrier gas adopts nitrogen; The pulse train of each deposition cycle is: trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purge, and the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
5. the preparation method of the conductive film that a kind of nano-stack according to claim 3 is transparent, it is characterized in that: step (4) is passed through completely independently pipeline and carry diethyl zinc in a pulsed fashion in cavity, the steam of trimethyl aluminium and deionized water, carrier gas adopts nitrogen; The pulse train of each deposition cycle of ZnO is: diethyl zinc pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purge, and the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds; Al 2o 3the pulse train of each deposition cycle is: trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purge, and the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
6. the preparation method of the conductive film that a kind of nano-stack according to claim 3 is transparent, is characterized in that: the doping level of the aluminium oxide that the frequency n 1 of circulation, n2, n3 collocation reach with practical application needs in the transparent conductive film of described nano-stack is as the criterion; Wherein, the scope of the scope of the frequency n 1 of circulation to be the scope of 1-100, n2 be 1-10, n3 is 1-1000.
7. the preparation method of the conductive film that a kind of nano-stack according to claim 3 is transparent, it is characterized in that: in step (6), after being circulated throughout of deposition plating, also can increase the step of annealing before cavity cooling, the annealing temperature that required annealing time needs with practical application is as the criterion.
8. conductive film transparent for nano-stack is used for the application of the passivation layer in solar cell by one kind, it is characterized in that: the conductive film that described nano-stack is transparent adopts the method preparation of any one claim in the claims, the conductive film that nano-stack described in when n-type is adulterated is transparent is used for the field passivation of cell p emitter, and the conductive film that the nano-stack described in when p-type adulterates is transparent is used for the field passivation of battery n emitter.
9. a kind of application conductive film transparent for nano-stack being used for the passivation layer in solar cell according to claim 8, is characterized in that: the conductive film that described nano-stack is transparent mainly comprises by ZnO layer and Al 2o 3the elementary cell of layer composition; The cycle-index of elementary cell itself is n3; In elementary cell, in ZnO layer, the cycle-index of ZnO individual layer is n1, Al 2o 3al in layer 2o 3the cycle-index of individual layer is n2; The gross thickness of film is n3 × (thickness × n1+Al of ZnO individual layer 2o 3thickness × the n2 of individual layer); The doping level of aluminium oxide in the transparent conductive film of described nano-stack is n2/ (n1+n2) at%; Wherein, the frequency n 1 of circulation and the scope of n2 are the scope of 1-100 and 1-10, n3 is respectively 1-1000.
10. a kind of application conductive film transparent for nano-stack being used for the passivation layer in solar cell according to claim 8, is characterized in that: the scope of the gross thickness of the conductive film that described nano-stack is transparent is between 5 nanometers to 200 nanometers.
A kind of application conductive film transparent for nano-stack being used for the passivation layer in solar cell described in 11. according to Claim 8 to 10, it is characterized in that: when the technique vacuum when preparing film in step (2) is 100 handkerchiefs, technological temperature is 200 degrees Celsius, the thickness of ZnO individual layer is 0.12nm, Al 2o 3the thickness of individual layer is 0.1nm; When the aluminium doping level of the transparent conductive film of described nano-stack is between 1.0at% to 7.1at%, the resistivity of film is 1.5 × 10 -3ohmcm is to 3.0 × 10 -3between ohmcm.
CN201610081430.XA 2016-02-05 2016-02-05 Method, material and application for solar energy battery surface passivation and current collection Pending CN105514182A (en)

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