CN106981539A - A kind of preparation method and application of nano-stack conductive film - Google Patents

A kind of preparation method and application of nano-stack conductive film Download PDF

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Publication number
CN106981539A
CN106981539A CN201710063481.4A CN201710063481A CN106981539A CN 106981539 A CN106981539 A CN 106981539A CN 201710063481 A CN201710063481 A CN 201710063481A CN 106981539 A CN106981539 A CN 106981539A
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conductive film
nano
stack
transparent conductive
preparation
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李翔
黎微明
潘景伟
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Jiangsu Weidao Nano Equipment Technology Co Ltd
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Jiangsu Weidao Nano Equipment Technology Co Ltd
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Publication of CN106981539A publication Critical patent/CN106981539A/en
Priority to PCT/CN2018/074886 priority Critical patent/WO2018141249A1/en
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    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
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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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Abstract

The invention belongs to field of semiconductor devices, and in particular to solar cell manufactures field, more particularly to prepares the preparation method of the transparent conductive film of nano-stack and the application in solar cell surface passivation and electric current collection with reference to technique for atomic layer deposition.For the technological process of existing PERC battery technologies, the metal oxide nano lamination conductive film prepared using technique for atomic layer deposition is as passivation layer, so as to the problem of solving dead resistance and big contact resistance, lift battery conversion efficiency, and suitable for producing in enormous quantities.

Description

A kind of preparation method and application of nano-stack conductive film
Technical field
This patent belongs to field of semiconductor devices, and in particular to solar cell manufactures field, more particularly to combines atom Layer deposition techniques prepare the preparation method of the transparent conductive film of nano-stack and received in solar cell surface passivation and electric current The application of concentration.
Background technology
Surface passivation is to reduce surface recombination rate, the important technical of the conversion efficiency of raising silicon solar cell. (Solar Energy Materials＆Solar Cells, 2006, (90):82-92) passivation emitter rear-face contact technology (PERC technologies), does backside passivation layer with PECVD method plating alundum (Al2O3) film after surface flocking and diffusion, arranges in pairs or groups Silicon nitride film anti-reflection layer.Because alundum (Al2O3) and silicon nitride are insulating materials, follow-up silver paste aluminium paste electrode will be by swashing The method and silicon face of light punching are connected.But the area of laser beam drilling is limited, so the dead resistance of electrode and silicon Influence whether the collection of electric current to influence the efficiency of battery, and the technique that partially perforation causes PERC technologies with contact resistance Complexity, and partially perforation also results in tapping in the presence of compound phenomenon.German Fraunhofer solar energy research institute (Fraunhofer ISE) devises contact passivating technique：Passivation layer is that one layer of ultra-thin silica and one layer of doping silicon thin layer are constituted Passivation, without perforate, the conduction of passivation layer is realized by metal oxide tunneling effect, but passivation layer is very thin in itself, needed The technique wanted is relative complex.Therefore, on the basis of PERC technologies, in addition it is also necessary to develop the surface passivation side without partially perforation Method.
Another scheme is to replace alundum (Al2O3) as passivation layer using conductive material, is expected to solve parasitism The problem of resistance and big contact resistance, lift battery conversion efficiency.Transparent conductive oxide (TCO) is as electrode material in photoelectricity Devices field is widely applied, and the zinc oxide (Aluminum doped Zinc oxide, AZO) of wherein aluminium doping has Preparation technology is simple, easily realize the features such as adulterating, and has document (Solar Energy, 2014 (110), 595-602) report, passes through AZO prepared by wet method has certain passivation properties, but technique prepared by wet method is complex, is not suitable for large-scale production. Technique for atomic layer deposition (ALD technique) is a kind of advanced film growth techniques.It is excellent, suitable using ALD technique processability The transparent conductive oxide material of passivation layer is done in PERC technologies, and there is not been reported.
The content of the invention
1st, the technical problems to be solved by the invention
The present invention be directed to the technological process of existing PERC battery technologies, it is processed using ALD technique, directly using can Conductive transparent material layer is as passivation layer, so that the problem of solving dead resistance and big contact resistance, lifts battery conversion efficiency, And suitable for producing in enormous quantities.
2nd, the technical scheme that the present invention is provided
The transparent conductive film of nano-stack based on technique for atomic layer deposition (ALD) preparation, for solar cell table The passivation in face and electric current collection.Specific technical scheme is as follows：
The preparation method of the transparent conductive film of nano-stack, is prepared using technique for atomic layer deposition, is specifically included Following main step：
(1) it will remove to carry on the back the silicon cell closed after washing and be loaded into the cavity of plated film, the face for needing plated film is in cavity Exposed state, it is not necessary to blocked in the face of plated film；
(2) the technique vacuum that cavity is vacuumized in simultaneously holding chamber body is constant, and it is required that heating reaches the temperature in cavity Technological temperature；
(3) 1~200 Al is circulated2O3Be deposited as transition zone, corresponding thickness range is 0.1-20 nanometers；
(4) n1 ZnO deposition is circulated, n2 Al is circulated2O3Deposition, wherein n1, n2 is non-zero positive integer；
(5) repeat step (4), the nano-stack conductive film of thickness needed for preparing；
(6) cavity directly cools or increased and cools after annealing steps, and vacuum breaker takes out silicon cell.
5~20 Al of preferred cycle in step (3)2O3Sedimentary be used as transition zone.Optimal cycle-index is 10 times. The effect of this transition zone is that chemical bond passivation and field-effect passivation, the particularly negative electrical charge in transition zone are carried out to silicon face, is deposited It is in the 1-3 nanometer ranges of interface, can effectively repels the electronics of silicon face, reduces hole with electronics near interface It is compound, so as to lift the open-circuit voltage and photoelectric transformation efficiency of battery.Because nano-stack plays a part of electric current collection simultaneously, So transition zone can not be hindered electric current while passivation is ensured by being formed.When the thickness of transition zone aluminum oxide film exists At less than 2 nanometers, electric current can be in the form of tunnelling directly through not having obstruction.The preferred thickness range of corresponding transition zone It is 0.5-2 nanometers.
Specifically, when being processed in step (1) to multi-disc silicon cell：In cell backside plated film, by multi-disc electricity Pond is put and compressed face-to-face, in battery front side plated film, is put two panels battery is back-to-back and is compressed, to save process chamber Space, increase production capacity.
Specifically, the range of choice of the technique vacuum in step (2) is 100 handkerchiefs to 1000 handkerchiefs, the selection model of technological temperature Enclose for 100-300 degrees Celsius.
Specifically, step (3) conveys trimethyl aluminium into cavity by completely self-contained pipeline and gone in a pulsed fashion The steam of ionized water, carrier gas uses nitrogen；The pulse train of deposition cycle is every time：Trimethyl aluminium pulse, nitrogen purging, go from The pulse of sub- water vapour, nitrogen purging, the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
Specifically, step (4) conveys diethyl zinc, front three into cavity in a pulsed fashion by completely self-contained pipeline The steam of base aluminium and deionized water, carrier gas uses nitrogen；The pulse train of each deposition cycles of ZnO is：Diethyl zinc pulse, nitrogen Air-blowing is swept, the pulse of deionized water steam, nitrogen purging, the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds；Al2O3Deposit every time The pulse train of circulation is：Trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purging, the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
Specifically, the preferred scope of the frequency n 1 of circulation is 1-100, and n2 preferred scope is 1-10.
Specifically, in step (6), after being circulated throughout of deposition plating, the step of annealing can also be increased before cavity cooling Suddenly, required annealing time is defined by the annealing temperature that practical application needs.Such as 500 degrees Celsius of annealing temperature uses 30 points The annealing of clock.
The application for the passivation layer that the transparent conductive film of nano-stack is used in solar cell, nano-stack is transparent Conductive film is prepared using the above method, and when n-type is adulterated, the transparent conductive film of nano-stack can be used for cell p emitter stage Field passivation, in p-doping the transparent conductive film of nano-stack be used for battery n emitter stages field be passivated.
Specifically, the transparent conductive film of described nano-stack mainly includes by ZnO layer and Al2O3It is basic that layer is constituted Unit；The cycle-index n3 × (thickness of ZnO individual layers × ZnO individual layers circulation of gross thickness=elementary cell of conductive film in itself Frequency n 1+Al2O3Thickness × Al of individual layer2O3Individual layer cycle-index n2)；Aluminum oxide is in the transparent conduction of described nano-stack Doping level in film is n2/ (n1+n2) at%.
Specifically, the scope of the gross thickness of the transparent conductive film of nano-stack is between 5 nanometers to 200 nanometers.
More specifically, the handkerchief of technique vacuum 100, technological temperature when preparing film in step (2) are 200 degrees Celsius, ZnO The thickness of individual layer be 0.12nm, error range ± 0.01nm (can be different according to different method of testings and instrument error scope, In the acceptable error range of those skilled in the art, similarly hereinafter), Al2O3The thickness of individual layer be 0.1nm, error range ± 0.01nm；On this condition, when the transparent conductive film of nano-stack aluminium doping level between 1.0at% to 7.1at% (this Place includes endpoint value) when, the resistivity of film is 1.5 × 10-3Ohmcm to 3.0 × 10-3(wrapped herein between ohmcm Include endpoint value).
The transparent conductive film of the nano-stack prepared using the above method is used to the solar cell for PERC structures In back of the body passivation layer, make field passivation of type n semiconductor material available in p+ emitter stages, or in n+ emitter stages p-type half Conductor material does field passivation.Passivation effect is than traditional Al-BSF battery (such as Solar Energy, 2014 (110), 595-602) 0.8% can be at least lifted in photoelectric transformation efficiency, electric conductivity can accomplish the Al-BSF battery directly contacted with sial Quite.
On the material that other can be used, by taking AZO as an example, the material such as B, Al, Ga, In of ZnO doping three races；Or Seven races' material such as Cl, I can become type n semiconductor material.The material of ZnO doping first family such as Li, Na, K；Or the 5th race Material such as N, P, As can become p-type semi-conducting material.
3rd, beneficial effect：
(1) back of the body that the transparent conductive film of the nano-stack of this patent preparation is used in the solar cell of PERC structures is blunt Change layer, passivation effect can at least lift 0.8% than traditional Al-BSF battery in photoelectric transformation efficiency, electric conductivity can be with Accomplish that the Al-BSF battery directly contacted with sial is suitable.
(2) Al of PERC batteries2O3Passivation is to be based on Al2O3The interface passivation effect that the negative electrical charge of internal institute's band reaches Should.ZnO inherently n-type semiconductors, more free electrons can be provided to reach its resistivity of reduction by being adulterated by Al Effect.
(3) passivation layer, the conversion efficiency for the reduction solar cell that will not shut out the light are used as using transparent conductive oxide.
Brief description of the drawings
The cyclic sequence of the transparent conductive film of Fig. 1 nano-stacks
The example that the transparent conductive film of Fig. 2 nano-stacks is applied with the passivation on p-type PERC batteries.
The example that the transparent conductive film of Fig. 3 nano-stacks is applied with the passivation on n-type battery.
Embodiment
With reference to Figure of description and specific embodiment, the present invention is described in detail.
Embodiment 1
Different process conditions (technique vacuum, technological temperature), different proportioning (n1, n2, n3 numbers are used in this patent Value, the doping level of aluminum oxide (n2/ (n1+n2) at%), the film for preparing heterogeneity (thickness, resistivity), specific each ginseng Several relations is as follows：
The table of comparisons between the preparation condition of table 1, composition and property
Embodiment 2
In order to realize the purpose of the present invention, it is more convenient for collected current using the relatively low material of resistivity, considers preparation The factors such as condition, proportioning, under conditions of the handkerchief of technique vacuum 100,200 degrees Celsius of technological temperature, fixed n2=1, control oxidation When the doping level of aluminium in the film is between 1at% to 7at%, the resistivity of film is smaller, 1.5 × 10-3Ohmcm is arrived 3.0×10-3Change between ohmcm, and with 1.5 × 10 in experiment-3Ohmcm is a minimum measured value.
The table of comparisons between preparation condition, composition and the property of the preferred embodiment of table 2
Embodiment 3
The transparent conductive film of the nano-stack prepared using this patent method is used for the solar cell of PERC structures In emitter stage passivation.Shown in reference picture 2, the zinc-oxide film adulterated with aluminium replaces the alumina layer in PERC batteries, its institute It is negatively charged to play a part of passivation to the p emitter stages at the back side.Meanwhile, this conductive film can play a part of collected current, Reduction is because of the small and elevated contact resistance of perforated area.The upper surface of this battery can also make of the transparent conductive film of p-doping Passivation.
Embodiment 4
The transparent conductive film of the transparent nano-stack prepared using this patent method is used for n-type crystal silicon solar Emitter stage passivation in battery.Shown in reference picture 3, the zinc-oxide film adulterated with aluminium is passivated to battery upper surface p emitter stages.Together When, this conductive film can play a part of collected current, and this film is less in the absorption of visible frequency, does not interfere with light Transmission.The back side of this battery can be also passivated with the transparent conductive film of p-doping.
The creation and embodiments thereof schematically to the present invention are described above, and protection scope of the present invention includes But it is not limited to the description above.Shown in accompanying drawing is also one of embodiment of the invention, and actual structure is not It is confined to this.So, if one of ordinary skill in the art is enlightened by the present invention, do not departing from the creation ancestor of the present invention In the case of purport, the frame mode similar to technical scheme and embodiment are designed without creative, all should be belonged to In the protection domain of this patent.

Claims (12)

1. a kind of preparation method of the transparent conductive film of nano-stack, it is characterised in that：Carried out using technique for atomic layer deposition Prepare, specifically include following main step：
(1) it will remove to carry on the back close after washing silicon cell and be loaded into the cavity of plated film, need the face of plated film in cavity in exposure State, it is not necessary to blocked in the face of plated film；
(2) the technique vacuum that cavity is vacuumized in simultaneously holding chamber body is constant, and heating makes the temperature in cavity reach required work Skill temperature；
(3) circulate 1~200 Al2O3 is deposited as transition zone；
(4) n1 ZnO deposition is circulated, n2 Al2O3 deposition is circulated, wherein n1, n2 is non-zero positive integer；
(5) repeat step (4), the nano-stack conductive film of thickness needed for preparing；
(6) cavity directly cools or increased and cools after annealing steps, and vacuum breaker takes out silicon cell.
2. a kind of preparation method of the transparent conductive film of nano-stack according to claim 1, it is characterised in that：Step (3) 5~20 Al of circulation in2O3Sedimentary be used as transition zone.
3. a kind of preparation method of the transparent conductive film of nano-stack according to claim 1, it is characterised in that：In step When being processed suddenly in (1) to multi-disc silicon cell：In cell backside plated film, multi-disc battery is put and compressed face-to-face, In battery front side plated film, put two panels battery is back-to-back and compresses, to save the space of process chamber, increase production capacity.
4. a kind of preparation method of the transparent conductive film of nano-stack according to claim 1 or 2 or 3, its feature exists In：The range of choice of technique vacuum in step (2) is 100 handkerchiefs to 1000 handkerchiefs, and the range of choice of technological temperature is taken the photograph for 100-300 Family name's degree.
5. a kind of preparation method of the transparent conductive film of nano-stack according to claim 4, it is characterised in that：Step (3) trimethyl aluminium and the steam of deionized water are conveyed into cavity by completely self-contained pipeline in a pulsed fashion, carrier gas is adopted Use nitrogen；The pulse train of deposition cycle is every time：Trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen Purging, the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds.
6. a kind of preparation method of the transparent conductive film of nano-stack according to claim 4, it is characterised in that：Step (4) diethyl zinc, the steaming of trimethyl aluminium and deionized water are conveyed into cavity by completely self-contained pipeline in a pulsed fashion Vapour, carrier gas uses nitrogen；The pulse train of each deposition cycles of ZnO is：Diethyl zinc pulse, nitrogen purging, deionized water are steamed The pulse of vapour, nitrogen purging, the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 seconds；Al2O3The pulse train of deposition cycle is every time： Trimethyl aluminium pulse, nitrogen purging, the pulse of deionized water steam, nitrogen purging, the time is respectively 0.1 second, 2 seconds, 0.1 second, 2 Second.
7. a kind of preparation method of the transparent conductive film of nano-stack according to claim 4, it is characterised in that：N1's Scope is 1-100, and n2 scope is 1-10.
8. a kind of preparation method of the transparent conductive film of nano-stack according to claim 4, it is characterised in that：In step Suddenly in (6), after being circulated throughout of deposition plating, the step of can also increasing annealing before cavity cooling, required annealing time with The annealing temperature that practical application needs is defined.
9. a kind of application for the passivation layer that conductive film that nano-stack is transparent is used in solar cell, it is characterised in that： The transparent conductive film of the nano-stack uses the method for any one claim in the claims to prepare, in n-type The field that the transparent conductive film of nano-stack described in during doping is used for cell p emitter stage is passivated, described in p-doping The field that the transparent conductive film of nano-stack is used for battery n emitter stages is passivated.
10. the passivation that a kind of conductive film that nano-stack is transparent according to claim 9 is used in solar cell The application of layer, it is characterised in that：The transparent conductive film of described nano-stack mainly includes by ZnO layer and Al2O3Layer composition Elementary cell；The cycle-index n3 × (thickness of ZnO individual layers × ZnO individual layers of gross thickness=elementary cell of conductive film in itself Cycle-index n1+Al2O3Thickness × Al of individual layer2O3Individual layer cycle-index n2)；Aluminum oxide is transparent in described nano-stack Doping level in conductive film is n2/ (n1+n2) at%.
11. the passivation that a kind of conductive film that nano-stack is transparent according to claim 9 is used in solar cell The application of layer, it is characterised in that：The scope of the gross thickness of the transparent conductive film of described nano-stack is received at 5 nanometers to 200 Between rice.
12. a kind of conductive film that nano-stack is transparent according to claim 9 to 11 is used in solar cell The application of passivation layer, it is characterised in that：Technique vacuum when preparing film in step (2) is that 100 handkerchiefs, technological temperature are 200 Degree Celsius when, the thickness of ZnO individual layers is 0.12nm, Al2O3The thickness of individual layer is 0.1nm；Led when described nano-stack is transparent When the aluminium doping level of conductive film is between 1.0at% to 7.1at%, the resistivity of film is 1.5 × 10-3Ohmcm to 3.0 × 10-3Between ohmcm.
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