CN104505461B - Multilayer anti-reflection film mixed solar cell base on organic polymer, and preparation method - Google Patents
Multilayer anti-reflection film mixed solar cell base on organic polymer, and preparation method Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 111
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 239000004065 semiconductor Substances 0.000 claims abstract description 42
- 238000004528 spin coating Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 19
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 19
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 81
- 230000003667 anti-reflective effect Effects 0.000 claims description 60
- 239000010936 titanium Substances 0.000 claims description 34
- 230000004888 barrier function Effects 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 26
- 239000010931 gold Substances 0.000 claims description 25
- 229920002120 photoresistant polymer Polymers 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 23
- 238000001259 photo etching Methods 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005566 electron beam evaporation Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 7
- 238000003475 lamination Methods 0.000 claims description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 238000011161 development Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 238000001020 plasma etching Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 claims 2
- 238000005229 chemical vapour deposition Methods 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 238000005137 deposition process Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229920000144 PEDOT:PSS Polymers 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002310 reflectometry Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 57
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 21
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 12
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 7
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000035772 mutation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000013742 energy transducer activity Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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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
- Y02E10/549—Organic 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
Landscapes
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a multilayer anti-reflection film mixed solar cell base on an organic polymer, and a preparation method, and belongs to the technical field of solar cells. The structure of the solar cell comprises a single-crystal semiconductor substrate, an insulating layer, a lower electrode, a first anti-reflection film, a hole conduction layer, an upper electrode, and a second anti-reflection film, wherein the single-crystal semiconductor substrate, the insulating layer, the lower electrode, the first anti-reflection film, the hole conduction layer, the upper electrode and the second anti-reflection film are sequentially stacked together. Moreover, the solar cell is in a planar structure. The first anti-reflection film is a titanium oxide layer prepared through a method of atomic layer deposition, and the thickness of the first anti-reflection film is from 0.5 nm to 1.5 nm. The hole conduction layer employs a PEDOT: PSS film formed by the spin coating of a PEDOT: PSS material. The second anti-reflection film is an alumina film growing through the method of atomic layer deposition or a polymethyl methacrylate film formed through spin coating, and the thickness of the second anti-reflection film is from 30 nm to 50 nm. The solar cell can greatly reduce the reflectivity of sunlight, can improve the efficiency and stability, is simple in manufacture technology, is low in cost, and is good in stability.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of to be based on poly- 3, the 4- ethylenes of new organic polymer
Dioxy thiophene/poly styrene sulfonate (PEDOT:The structure design and technology of preparing of hybrid solar cell PSS).
Background technology
Traditional Si based solar battery in occupation of civilian photovoltaic market, however, due to the high shortcoming of manufacturing cost, greatly
Limit the development of photovoltaic products.Thus, novel solar battery, such as Si bases hybrid solar cell, organic thin film cells,
Because the space of its low cost, improved efficiency is big, the extensive concern of researcher is caused in recent years, become area of solar cell new
Research direction.Wherein, new material and single crystal semiconductor substrate are combined to form mixing based on heterojunction structure too
Positive energy battery, for example, PEDOT:PSS/Si, Graphene/Si, CNT/Si etc., combine single crystal semiconductor and new material
Respective advantage so that inexpensive, efficient solaode is possibly realized.
Organic polymer PEDOT:PSS is a kind of macromolecule polymer material, and it possesses high hole conductivity, high permeability
And the good characteristic such as high machinery ductility, it is widely used in organic thin film cells and hybrid solar cell research field.
In hybrid solar cell, PEDOT:PSS contacts to form hetero-junctions as hole transmission layer with single crystal semiconductor substrate, produces
Space charge depletion region, photo-generated carrier is separated in depletion region and forms photoelectric current.PEDOT:PSS solution and single crystal semiconductor shape
Into PEDOT:PSS/ single crystal semiconductors hybrid solar cell only needs easy spin coating and heat curing process, is conducive to being prepared into
This reduction.
The photoelectric transformation efficiency of solaode depends on many factors, wherein, the reflection for reducing incident illumination is to improve too
The effective way of positive energy battery efficiency.At present, one of method for generally adopting in battery surface to prepare light trapping structure.The sunken light
Structure causes incident ray before the external world is reflected back, and multiple reflections are carried out inside it, increases the propagation path of light, strengthens
Absorption of the quasiconductor to incident illumination, so as to be beneficial to improve the energy conversion efficiency of solaode.The research that the applicant is located
Group is in patent (patent publication No.:CN102263144B the bionical moth ocular structure of column proposed in) and Taiwan Univ. Wan-Rou
Wei et al. is in paper " Omnidirectional Harvesting Characteristics by
EmployingHierarchical Photon-Trapping Structures(Nano Lett.2013,13,3658-
3663) " silicon pyramid+nano wire " layering photon capture structure proposed in " is the representative instance of surface light trapping structure, this
Two kinds of structures can greatly reduce the reflection of sunlight.But, preparing these surface textures needs wet etching and photoetching
Technique, and based on PEDOT:In PSS hybrid solar cells field, the excessively small surface texture of size is unfavorable for
PEDOT:PSS forms therewith preferably contact, and the raising of battery efficiency can be negatively affected on the contrary.
The content of the invention
The purpose of the present invention is to overcome the weak point of prior art, there is provided one kind is based on organic polymer
(PEDOT:PSS multilamellar antireflective film hybrid solar cell (structure)) and preparation method;Using multilamellar antireflective film, can be significantly
The reflectance of sunlight is reduced, the efficiency and stability test of solaode can be improved, and possess preparation process is simple, cost
It is cheap and the features such as have good stability.
The present invention proposes a kind of multilamellar antireflective film hybrid solar cell structure based on organic polymer, and its feature exists
In the solar battery structure includes:According to the single crystal semiconductor substrate that preparation order is stacked gradually, insulating barrier, bottom electrode,
One antireflective film, Hole transporting layers, Top electrode, the second antireflective film, and the hybrid solar cell are planar structure;First anti-reflection
Film is the titanium oxide (TiO prepared using atomic layer deposition method2) thin layer, thickness is 0.5nm~1.5nm;The Hole transporting layers
Using PEDOT:The PEDOT that the spin coating of PSS materials is formed:PSS thin film;Second antireflective film is to be given birth to by atomic layer deposition method
Long aluminium oxide (Al2O3) film or by spin coating formed polymethyl methacrylate (PMMA) film, thickness be 30~50nm.
The single crystal semiconductor substrate is single crystal semiconductor silicon (Si) or GaAs (GaAs);Insulating barrier is using thermal oxide side
Method or the silicon oxide (SiO of plasma enhanced chemical vapor deposition method (PECVD) deposit2) or silicon nitride (Si3N4);Lower electricity
Titanium/palladium/gold (Ti/Pd/Au) that extremely prepared by electron beam evaporation methods, or titanium/palladium/silver (Ti/Pd/Ag) laminated construction;Upper electricity
Titanium/gold (the Ti/ for extremely brushing the silver electrode of elargol formation or being formed by electron beam evaporation methods after being blocked using hard mask
Au) laminated construction.
The present invention also proposes a kind of method for preparing above-mentioned solar battery structure, it is characterised in that methods described includes
Following steps:
1) single crystal semiconductor substrate is cleaned:With proportioning 1:4 hydrogen peroxide and concentrated sulphuric acid mixed liquor are at a temperature of 80~85 DEG C
10~15min is boiled, surface blot is removed, then deionized water rinses 10~15min, dry for standby;Wherein, single crystal semiconductor
Substrate is that N-type phosphorus doping list throws the single throwing GaAs lining of silicon substrate, (100) crystal orientation, the Ω cm of resistivity 1~10, or the doping of N-type silicon
Bottom, (100) crystal orientation, 1~10E17cm of carrier concentration-3;
2) insulating barrier is grown:
2.1) method 1:The SiO deposited in the front of single crystal semiconductor substrate using PECVD methods2Or Si3N4, thickness is
200~300nm, or
2.2) method 2:When single crystal semiconductor substrate is single crystal Si substrate, using the SiO of thermal oxidation process growth2, thickness
For 200~300nm, after the completion of oxidation, by positive SiO2Layer is protected with photoresist, with buffered oxide etchant BOE (6:
1)(H2O:HF) solution 2~3min of ultrasound under ultrasound environments removes the SiO at the back side2Layer, then repeatedly with acetone-ethanol-go from
Sub- water washes off photoresist;
3) bottom electrode is prepared:Ti/Pd/Au electrodes are deposited with successively at the single crystal semiconductor substrate back side using e-beam evaporation
Or Ti/Pd/Ag electrodes, thickness is respectively 5~10/10~20/30~50nm;
4) photoetching:Single crystal semiconductor substrate front after to completing 3) technique carries out photoetching process and develops battery window region
Domain;First bottom electrode is protected with photoresist;Then front spin coating photoresist, 3000~5000rpm, 30~60s;Front baking
100~120 DEG C, 1~3min;3~5s of exposure;Development;100~120 DEG C of after bake, 10~15min is standby;Exposed portion is
Battery window region;
5) etch:After the completion of photoetching process, the insulating barrier of battery window region, etching are etched using reactive ion etching method
200~300nm of thickness;After the completion of etching, photoresist is removed with acetone-ethanol-deionized water rinsing repeatedly;
6) the first antireflective film is prepared:After the completion of etching technics, deposited on battery window area insulating barrier using ALD methods
Antireflective film, material is TiO2, thickness is 0.5nm~1.5nm;
7) Hole transporting layers are prepared:Hole transporting layers PEDOT is prepared on the first antireflective film 4 using spin coating method:PSS,
Spin coating speed and time are followed successively by:600~1000rpm/10~15s;3000~5000rpm/60~100s, is then placed in baking oven
In, 10~15min is toasted at 120~140 DEG C, solidify Hole transporting layers;
8) Top electrode is prepared:
8.1) method 1:If upper electrode material is Ag glue, Ag glue is uniformly brushed in hole conduction using the method brushed
Layer is covered in the region on insulation layer, natural air drying;Or
8.2) method 2:If upper electrode material is Ti/Au laminations, using electron beam evaporation methods, with hard mask battery is blocked
Window region, is deposited with successively Ti, Au layer, and thickness is respectively 5~10nm, 30~50nm;
9) the second antireflective film is prepared:
9.1) method 1:If anti-reflection membrane material is PMMA, using spin coating method on the battery sample for completing Top electrode preparation
PMMA film layer is prepared, then 4000~6000rpm/30~60s toasts 5~10min post bakes at 85~100 DEG C;It is prepared by battery
Complete;Or
9.2) method 2:If anti-reflection membrane material is Al2O3, using ALD methods on the battery sample for completing Top electrode preparation
Prepare Al2O3Film layer, thickness is 30~50nm.Battery is prepared and completed.
It is above-mentioned based on new organic polymer (PEDOT:PSS multilamellar antireflective film hybrid solar cell structure) have with
Under several features:
(1) designed using two-layer antireflective film, the reflectance of sunlight can be greatly decreased, be conducive to solar battery efficiency
Raising;
(2) antireflective film adopts TiO2Material, in addition to providing anti-reflection effect, its good moistening is conducive to PEDOT:PSS
Aqueous solution preferable film forming in the single crystal semiconductor substrate of hydrophobic, forms preferable heterojunction.Additionally, TiO2Light urge
Change effect and enable photon formation photo-generated carrier of the energy absorption more than or equal to its energy gap (3.2eV), be conducive to
Improve the external quantum efficiency of solaode.
(3) the PEDOT that Hole transporting layers are adopted:PSS materials, produce except forming heterojunction with single crystal semiconductor substrate
Outside third contact of a total solar or lunar eclipse electrical effect, its refractive index is between the first antireflective film and the second antireflective film, while also providing anti-reflection effect.
(4) the second anti-reflection membrane material adopts Al2O3Or PMMA materials, in addition to anti-reflection effect is provided, its good chemically stable
Property and weather resistance are preferably by PEDOT:PSS Hole transporting layers are encapsulated, and the outside circumstances not known of isolation is invaded organic layer
Erosion, improves stability test.
Summary, based on organic polymer PEDOT:The multilamellar antireflective film hybrid solar cell of PSS can effectively drop
The reflection of low sunlight, so as to reach the purpose of cell photoelectric conversion efficiency is improved, and possesses preparation process is simple, with low cost
And the features such as have good stability.
Description of the drawings
Fig. 1 is the present invention based on PEDOT:The structural representation of PSS multilamellar antireflective film hybrid solar cells.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is described in detail to the present invention.
It is proposed by the present invention based on organic polymer (PEDOT:PSS multilamellar antireflective film hybrid solar cell structure),
As shown in figure 1, the solar battery structure includes:According to the single crystal semiconductor substrate 1 that preparation order is stacked gradually, insulating barrier 2,
Bottom electrode 3, the first antireflective film 4, Hole transporting layers 5, Top electrode 6, the second antireflective film 7, and the hybrid solar cell are plane
Structure.
The single crystal semiconductor substrate 1 is single crystalline Si or GaAs;Insulating barrier 2 is using thermal oxidation process or PECVD methods
The SiO of deposit2Or Si3N4;Bottom electrode 3 is titanium Ti/Pd/Au or Ti/Pd/Ag laminated construction prepared by electron beam evaporation methods;The
One antireflective film 4 is the TiO prepared using ALD methods2Thin layer, thickness is 0.5nm~1.5nm;What Hole transporting layers 5 were adopted
PEDOT:The PEDOT that the spin coating of PSS materials is formed:PSS thin film;Ag electrodes or adopt hard that Top electrode 6 is formed for brushing elargol
The Ti/Au laminated construction that mask is formed after blocking by electron beam evaporation methods;Second antireflective film 7 is to be grown by ALD
Al2O3Film or the PMMA film formed by spin coating, thickness is 30~50nm.
It is proposed by the present invention based on organic polymer PEDOT:The base of the multilamellar antireflective film hybrid solar cell structure of PSS
Present principles are:In addition to the light trapping structure introduced in using background technology, the plane reflection rate for reducing light wave is also to improve the sun
Light utilization efficiency strengthens the effective measures of solar cell photoelectric conversion efficiency.The reflection of light generally occurs in the different thing of refractive index
On interface between matter, larger refractive index mutation can cause larger light to reflect.As planar structure silicon based cells, visible
Interior 1.0 mutation due to the refractive index of light from air of optical range are to 4.4 in Si, thus reflectance is up to more than 30%, makes
Into substantial amounts of energy loss.So, the reflectance of sunlight can be reduced by the mutation of reduction refractive index.In the present invention
Using refractive index of the material in visible-range be followed successively by:Al2O3About 1.76, PMMA is about 1.49, PEDOT:PSS is about
For 1.60, TiO2About 2.65, Si is about 4.40, GaAs and is about 3.28.The laminated construction that these materials are formed possesses refractive index
The characteristic of gradual change, can greatly reduce the reflectance of battery.Additionally, all battery structures are planar structure in the present invention, in reality
PEDOT is ensure that while existing anti-reflection effect:Formed between PSS and substrate and preferably contacted, it is ensured that the height of prepared battery
Performance.
It is proposed by the present invention prepare it is above-mentioned based on organic polymer PEDOT:The multilamellar antireflective film hybrid solar cell of PSS
Method, technological process comprises the following steps:
1) single crystal semiconductor substrate 1 is cleaned:With proportioning 1:4 hydrogen peroxide and concentrated sulphuric acid mixed liquor are at a temperature of 80~85 DEG C
10~15min is boiled, surface blot is removed, then deionized water rinses 10~15min, dry for standby;Wherein, single crystal semiconductor
Substrate 1 is that N-type phosphorus doping list throws Si wafers, (100) crystal orientation, the Ω cm of resistivity 1~10, or the single throwing GaAs of N-type Si doping
Wafer, (100) crystal orientation, 1~10E17cm of carrier concentration-3;
2) insulating barrier 2 is grown:
2.1) method 1:The SiO deposited in the front of single crystal semiconductor substrate 1 using PECVD methods2Or Si3N4, thickness is
200~300nm, or
2.2) method 2:If single crystal semiconductor substrate 1 is Si wafers, it would however also be possible to employ thermal oxidation process growth
SiO2, thickness is 200~300nm, and after the completion of oxidation, by positive silicon oxide, with photoresist (AZ601) is protected, with buffering
Oxide etch agent BOE (6:1)(H2O:HF) solution 2~3min of ultrasound under ultrasound environments removes the oxide layer at the back side, then instead
Multiplexing acetone-ethanol-deionized water rinsing removes photoresist;
3) bottom electrode 3 is prepared:Ti/Pd/Au is deposited with successively at the back side of single crystal semiconductor substrate 1 using e-beam evaporation electric
Pole or Ti/Pd/Ag electrodes, thickness is respectively 5~10/10~20/30~50nm;
4) photoetching:The front of single crystal semiconductor substrate 1 after to completing 3) technique carries out photoetching process and develops battery window
Region.In order to prevent photoetching process and follow-up etching technics destruction bottom electrode 3, first with photoresist (AZ601) enters to bottom electrode 3
Row protection.Then front spin coating photoresist AZ601,3000~5000rpm, 30~60s;100~120 DEG C of front baking, 1~3min;
3~5s of exposure;Development;100~120 DEG C of after bake, 10~15min is standby.Exposed portion is battery window region;
5) etch:After the completion of photoetching process, the insulating barrier 2 of battery window region is etched using reactive ion etching method, carved
Erosion 200~300nm of thickness;After the completion of etching, photoresist is removed with acetone-ethanol-deionized water rinsing repeatedly;
6) the first antireflective film 4 is prepared:After the completion of etching technics, formed sediment on battery window area insulating barrier 2 using ALD methods
Product antireflective film, material is TiO2, thickness is 0.5nm~1.5nm;
7) Hole transporting layers 5 are prepared:Hole transporting layers PEDOT is prepared on antireflective film 4 using spin coating method:PSS, spin coating
Speed and time are followed successively by:600~1000rpm/10~15s;3000~5000rpm/60~100s, is then put into baking oven by it
In, 10~15min is toasted at 120~140 DEG C, solidify Hole transporting layers 5;
8) Top electrode 6 is prepared:
8.1) method 1:The material of Top electrode 6 is elargol, is uniformly brushed elargol in hole conduction using the method brushed
Layer 5 is covered in the region on insulation layer 2, natural air drying;Or
8.2) method 2:The material of Top electrode 6 is Ti/Au laminations, using electron beam evaporation methods, with hard mask battery is blocked
Window region, is deposited with successively Ti, Au layer, and thickness is respectively 5~10nm, 30~50nm.
9) the second antireflective film 7 is prepared:
9.1) method 1:Anti-reflection membrane material is PMMA, using spin coating method on the battery sample for completing the preparation of Top electrode 6
PMMA film layer is prepared, then 4000~6000rpm/30~60s toasts 5~10min post bakes at 85~100 DEG C.It is prepared by battery
Complete;
9.2) method 2:Anti-reflection membrane material is Al2O3, made on the battery sample for completing the preparation of Top electrode 6 using ALD methods
Standby Al2O3Film layer, thickness is 30~50nm.Battery is prepared and completed.
Embodiment 1:
Embodiment 1 is the representative instance of present invention.
The present embodiment based on organic polymer PEDOT:The multilamellar antireflective film hybrid solar cell structure of PSS includes single
Brilliant Semiconductor substrate 1, insulating barrier 2, bottom electrode 3, the first antireflective film 4, Hole transporting layers 5, Top electrode 6, the second antireflective film 7, and
Battery surface is planar structure.Wherein, the single crystal semiconductor substrate 1 for adopting throws Si, (100) crystal orientation, resistivity 3~6 for N-type list
Ω cm, thickness 470um;Insulating barrier 2 is the 300nm thickness SiO of thermal oxide growth2Layer;Bottom electrode 3 is Ti/Pd/Au laminations, thick
Degree is followed successively by 5/10/30nm;Antireflective film 4 is the 0.5nm thickness TiO of ALD growths2Thin layer;Hole transporting layers 5 are for about 60nm thick
PEDOT:PSS films, the PEDOT for using:PSS (PH1000) solution is the production of He Lishi companies of Germany;Top electrode 6 is brushing elargol
The Ag electrodes of formation;Antireflective film 7 is 50nm thickness PMMA films prepared by spin coating.
The technological process of the present embodiment is:
1) single crystal Si substrate 1 is cleaned:With proportioning 1:4 hydrogen peroxide and concentrated sulphuric acid mixed liquor boil 10min at a temperature of 85 DEG C,
Surface blot is removed, then deionized water rinses 10min, dry for standby;
2) insulating barrier 2 is grown:The SiO grown using thermal oxidation process2, thickness is 300nm, after the completion of oxidation, by front
SiO2With photoresist (AZ601) is protected layer, with buffered oxide etchant BOE (6:1) solution ultrasound under ultrasound environments
3min removes the SiO at the back side2Layer, then repeatedly with acetone-ethanol-deionized water rinsing removal photoresist;
3) bottom electrode 3 is prepared:Ti/Pd/Au electrodes are deposited with successively at the back side of single crystal Si substrate 1 using e-beam evaporation,
Thickness is respectively 5/10/30nm;
4) photoetching:The front of single crystal Si substrate 1 after to completing 3) technique carries out photoetching process and develops battery window area.
In order to prevent photoetching process and follow-up etching technics destruction bottom electrode 3, first with photoresist (AZ601) is protected to bottom electrode 3
Shield.Then front spin coating photoresist AZ601,3000rpm, 60s;100 DEG C of front baking, 1min;Exposure 5s;Development;100 DEG C of after bake,
15min, it is standby.Exposed portion is battery window region;
5) etch:After the completion of photoetching process, the insulating barrier 2 of battery window region is etched using reactive ion etching method, carved
Erosion thickness 300nm;After the completion of etching, photoresist is removed with acetone-ethanol-deionized water rinsing repeatedly;
6) the first antireflective film 4 is prepared:After the completion of etching technics, formed sediment on battery window area insulating barrier 2 using ALD methods
Product antireflective film, material is TiO2, thickness is 0.5nm;
7) Hole transporting layers 5 are prepared:Hole transporting layers PEDOT is prepared on antireflective film 4 using spin coating method:PSS, spin coating
Speed and time are followed successively by:600rpm/15s;3000rpm/100s, is then put into it in baking oven, toasts at 120 DEG C
15min, solidifies Hole transporting layers 5;
8) Top electrode 6 is prepared:The material of Top electrode 6 is elargol, is uniformly brushed elargol in hole using the method brushed
Conductive layer 5 is covered in the region on insulation layer 2, natural air drying;
9) the second antireflective film 7 is prepared:Anti-reflection membrane material is PMMA, using spin coating method in the electricity for completing the preparation of Top electrode 6
PMMA film layer is prepared on the sample of pond, then 4000rpm/60s toasts 5min post bakes at 90 DEG C.Battery is prepared and completed;
Embodiment 2:
Embodiment 2 is the representative instance of present invention.
The present embodiment based on organic polymer PEDOT:The multilamellar antireflective film hybrid solar cell structure of PSS includes single
Brilliant Semiconductor substrate 1, insulating barrier 2, bottom electrode 3, the first antireflective film 4, Hole transporting layers 5, Top electrode 6, the second antireflective film 7, and
Battery surface is planar structure.Wherein, the single crystal semiconductor substrate 1 for adopting throws Si, (100) crystal orientation, resistivity 3~6 for N-type list
Ω cm, thickness 470um;Insulating barrier 2 is the 200nm thickness SiO of thermal oxide growth2Layer;Bottom electrode 3 is Ti/Pd/Au laminations, thick
Degree is followed successively by 10/20/50nm;Antireflective film 4 is the 1.5nm thickness TiO of ALD growths2Thin layer;Hole transporting layers 5 are for about 60nm thick
PEDOT:PSS films, the PEDOT for using:PSS (PH1000) solution is the production of He Lishi companies of Germany;Top electrode 6 is brushing elargol
The Ag electrodes of formation;Antireflective film 7 is 30nm thickness PMMA films prepared by spin coating.
The technological process of the present embodiment is:
1) single crystal Si substrate 1 is cleaned:With proportioning 1:4 hydrogen peroxide and concentrated sulphuric acid mixed liquor boil 15min at a temperature of 80 DEG C,
Surface blot is removed, then deionized water rinses 15min, dry for standby;
2) insulating barrier 2 is grown:The SiO grown using thermal oxidation process2, thickness is 200nm, after the completion of oxidation, by front
SiO2With photoresist (AZ601) is protected layer, with buffered oxide etchant BOE (6:1) solution ultrasound under ultrasound environments
2min removes the SiO at the back side2Layer, then repeatedly with acetone-ethanol-deionized water rinsing removal photoresist;
3) bottom electrode 3 is prepared:Ti/Pd/Au electrodes are deposited with successively at the back side of single crystal Si substrate 1 using e-beam evaporation,
Thickness is respectively 10/20/50nm;
4) photoetching:The front of single crystal Si substrate 1 after to completing 3) technique carries out photoetching process and develops battery window area.
In order to prevent photoetching process and follow-up etching technics destruction bottom electrode 3, first with photoresist (AZ601) is protected to bottom electrode 3
Shield.Then front spin coating photoresist AZ601,5000rpm, 30s;120 DEG C of front baking, 3min;Exposure 3s;Development;120 DEG C of after bake,
10min, it is standby.Exposed portion is battery window region;
5) etch:After the completion of photoetching process, the insulating barrier 2 of battery window region is etched using reactive ion etching method, carved
Erosion thickness 200nm;After the completion of etching, photoresist is removed with acetone-ethanol-deionized water rinsing repeatedly;
6) the first antireflective film 4 is prepared:After the completion of etching technics, formed sediment on battery window area insulating barrier 2 using ALD methods
Product antireflective film, material is TiO2, thickness is 1.5nm;
7) Hole transporting layers 5 are prepared:Hole transporting layers PEDOT is prepared on antireflective film 4 using spin coating method:PSS, spin coating
Speed and time are followed successively by:1000rpm/10s;5000rpm/60s, is then put into it in baking oven, toasts at 140 DEG C
10min, solidifies Hole transporting layers 5;
8) Top electrode 6 is prepared:The material of Top electrode 6 is elargol, is uniformly brushed elargol in hole using the method brushed
Conductive layer 5 is covered in the region on insulation layer 2, natural air drying;
9) the second antireflective film 7 is prepared:Anti-reflection membrane material is PMMA, using spin coating method in the electricity for completing the preparation of Top electrode 6
PMMA film layer is prepared on the sample of pond, then 6000rpm/30s toasts 5min post bakes at 90 DEG C.Battery is prepared and completed;
Embodiment 3:
The present embodiment is similar to the technical process of embodiment 2, and difference is:Step 8) prepare Top electrode 6 adopt electronics
Beam evaporation coating method, with hard mask battery window area is blocked, the titanium (Ti) formed in the region of insulating barrier 2/gold (Au) lamination knot
Structure, thickness is 5nm/30nm.Meanwhile, in step 9) prepare the Al that antireflective film 7 grows 30nm thickness using ALD methods2O3Layer.It is real
Example 3 is applied compared with embodiment 1 using standard technology, industrial extensively application is suitable to.
Embodiment 4:
The present embodiment is similar to the technical process of embodiment 2, and difference is:Step 8) prepare Top electrode 6 adopt electronics
Beam evaporation coating method, with hard mask battery window area is blocked, the titanium (Ti) formed in the region of insulating barrier 2/gold (Au) lamination knot
Structure, thickness is 10nm/50nm.Meanwhile, in step 9) prepare the Al that antireflective film 7 grows 50nm thickness using ALD methods2O3Layer.It is real
Example 4 is applied compared with embodiment 2 using standard technology, industrial extensively application is suitable to.
Embodiment 5:
The present embodiment is similar to the technical process of embodiment 3, and difference is;Step 1) in battery single crystal semiconductor lining
Bottom 1 GaAs wafers, (100) crystal orientation, 1~10E17cm of carrier concentration are thrown using the Si doping lists of N-type-3, thickness 450um.Together
When, insulating barrier 2 grows the Si of one layer of 300nm thickness using PECVD methods3N4.GaAs single crystalline substrates possess more compared with Si single crystalline substrates
High electron mobility, and it belongs to direct gap semiconductor, it is thus possible to obtain more preferably photoelectric transformation efficiency..This
Outward, the present embodiment adopts standard technology, is suitable to industrial extensively application.
Embodiment 6:
The present embodiment is similar to the technical process of embodiment 4, and difference is that the single crystal semiconductor substrate 1 of battery adopts N
The Si doping of type is single to throw GaAs wafers, (100) crystal orientation, resistivity 1~10 Ω cm, thickness 450um.Meanwhile, insulating barrier 2 is adopted
The Si of one layer of 300nm thickness is grown with PECVD methods3N4.GaAs single crystalline substrates possess higher electron transfer compared with Si single crystalline substrates
Rate, and it belongs to direct gap semiconductor, it is thus possible to obtain more preferably photoelectric transformation efficiency.Additionally, the present embodiment is equal
Using standard technology, industrial extensively application is suitable to.
Claims (3)
1. a kind of multilamellar antireflective film hybrid solar cell structure based on organic polymer, it is characterised in that the solar-electricity
Pool structure includes:According to the single crystal semiconductor substrate that preparation order is stacked gradually, insulating barrier, bottom electrode, the first antireflective film, hole
Conductive layer, Top electrode, the second antireflective film, and the hybrid solar cell are planar structure;First antireflective film is to adopt atom
Oxidation titanium lamina prepared by layer deposition process, thickness is 0.5nm~1.5nm;The PEDOT that the Hole transporting layers are adopted:PSS materials
The PEDOT that spin coating is formed:PSS thin film;Second antireflective film is the pellumina that grown by atomic layer deposition method or is passed through
The polymethyl methacrylate film that spin coating is formed, thickness is 30~50nm.
2. the multilamellar antireflective film hybrid solar cell structure of organic polymer is based on as claimed in claim 1, it is characterised in that
The single crystal semiconductor substrate is monocrystal silicon or GaAs;Insulating barrier is using thermal oxidation process or plasma enhanced chemical gas
The silicon oxide or silicon nitride of phase sedimentation deposit, thickness is 200~300nm;The titanium that bottom electrode is prepared for electron beam evaporation methods/
Palladium/gold, or titanium/palladium/silver laminated construction, thickness is respectively 5~10/10~20/30~50nm;Top electrode is formed to brush elargol
Silver electrode or titanium/gold laminated construction for being formed by electron beam evaporation methods after being blocked using hard mask.
3. a kind of side for preparing multilamellar antireflective film hybrid solar cell structure as claimed in claim 1 based on organic polymer
Method, it is characterised in that the method comprising the steps of:
1) single crystal semiconductor substrate is cleaned:With proportioning 1:4 hydrogen peroxide and concentrated sulphuric acid mixed liquor boil 10 at a temperature of 80~85 DEG C
~15min, removes surface blot, and then deionized water rinses 10~15min, dry for standby;Wherein, single crystal semiconductor substrate
Silicon substrate, (100) crystal orientation, the Ω cm of resistivity 1~10, or the single throwing gallium arsenide substrate of N-type silicon doping are thrown for N-type phosphorus doping list,
(100) crystal orientation, 1~10E17cm of carrier concentration-3;
2) insulating barrier is grown:
2.1) method 1:Using plasma strengthens front silicon oxide deposition of the chemical vapour deposition technique in single crystal semiconductor substrate
Or silicon nitride film layer, thickness is 200~300nm, or
2.2) method 2:When single crystal semiconductor substrate is monocrystal silicon, using thermal oxidation process growing silicon oxide film layer, thickness is 200
~300nm, after the completion of oxidation, positive silicon oxide layer is protected with photoresist, is existed with buffered oxide etchant BOE solution
2~3min of ultrasound removes the silicon oxide layer at the back side under ultrasound environments, then repeatedly with acetone-ethanol-deionized water rinsing removal
Photoresist, the buffered oxide etchant BOE solution is H2O:HF=6:1;
3) bottom electrode is prepared:Using e-beam evaporation the single crystal semiconductor substrate back side be deposited with successively titanium/palladium/gold electrode or
Titanium/palladium/silver electrode, thickness is respectively 5~10/10~20/30~50nm;
4) photoetching:Single crystal semiconductor substrate front after to completing 3) technique carries out photoetching process and develops battery window area;
First bottom electrode is protected with photoresist;Then front spin coating photoresist, 3000~5000rpm, 30~60s;Front baking 100~
120 DEG C, 1~3min;3~5s of exposure;Development;100~120 DEG C of after bake, 10~15min is standby;Exposed portion is battery window
Mouth region domain;
5) etch:After the completion of photoetching process, the insulating barrier of battery window area is etched using reactive ion etching method, etching is thick
200~300nm of degree;After the completion of etching, photoresist is removed with acetone-ethanol-deionized water rinsing repeatedly;
6) the first antireflective film is prepared:After the completion of etching technics, using atomic layer deposition method on battery window area insulating barrier
The first antireflective film is deposited, material is titanium oxide, and thickness is 0.5nm~1.5nm;
7) Hole transporting layers are prepared:Hole transporting layers PEDOT is prepared on the first antireflective film using spin coating method:PSS, spin coating speed
Degree and time are followed successively by:600~1000rpm/10~15s, and 3000~5000rpm/60~100s;In being then placed in baking oven,
10~15min is toasted at 120~140 DEG C, solidifies Hole transporting layers;
8) Top electrode is prepared:
8.1) method 1:If upper electrode material is elargol, elargol is equably brushed using the method brushed is covered in Hole transporting layers
In lid region on the insulating layer, natural air drying;Or
8.2) method 2:If Top electrode is titanium/gold lamination, using electron beam evaporation methods, with hard mask battery window region is blocked
Domain, is deposited with successively titanium, layer gold, and thickness is respectively 5~10nm, 30~50nm;
9) the second antireflective film is prepared:
9.1) method 1:If anti-reflection membrane material is polymethyl methacrylate, using spin coating method in the electricity for completing Top electrode preparation
Prepare 30~50nm thickness polymethyl methacrylate film layers on the sample of pond, 4000~6000rpm/30~60s, then 85~
5~10min post bakes are toasted at 100 DEG C;Battery is prepared and completed;Or
9.2) method 2:If anti-reflection membrane material is aluminium oxide, using atomic layer deposition method in the battery sample for completing Top electrode preparation
Aluminum oxide film layer is prepared on product, thickness is 30~50nm, and battery is prepared and completed.
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