CN105355787A - Novel solar cell device and preparation method thereof - Google Patents
Novel solar cell device and preparation method thereof Download PDFInfo
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- CN105355787A CN105355787A CN201510718503.7A CN201510718503A CN105355787A CN 105355787 A CN105355787 A CN 105355787A CN 201510718503 A CN201510718503 A CN 201510718503A CN 105355787 A CN105355787 A CN 105355787A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 111
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 111
- 239000004065 semiconductor Substances 0.000 claims abstract description 72
- 230000005540 biological transmission Effects 0.000 claims abstract description 54
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 195
- 238000004528 spin coating Methods 0.000 claims description 67
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 40
- 239000011521 glass Substances 0.000 claims description 34
- 229910021389 graphene Inorganic materials 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- XIQSOLVKPRJYKE-UHFFFAOYSA-M iodo(methylamino)lead Chemical compound CN[Pb]I XIQSOLVKPRJYKE-UHFFFAOYSA-M 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 238000009832 plasma treatment Methods 0.000 claims description 18
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 17
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- 239000011241 protective layer Substances 0.000 claims description 6
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 5
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000002096 quantum dot Substances 0.000 claims description 3
- 239000002238 carbon nanotube film Substances 0.000 claims description 2
- 239000002079 double walled nanotube Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 description 29
- 238000010276 construction Methods 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 description 15
- 238000000280 densification Methods 0.000 description 15
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- -1 comprises anode 7 Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/221—Carbon nanotubes
-
- 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
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- Manufacturing & Machinery (AREA)
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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a novel solar cell device and a preparation method thereof. The novel solar cell device comprises an anode, a cavity transmission layer, an active layer, an electron transmission layer, a transparent electrode and a substrate which are successively laid in layer. The cavity transmission layer is a one-layer structure formed by carbon nanotubes and P type semiconductors or a two-layer structure formed by a single carbon nanotube layer and P type semiconductor layer. Compared with the prior art, the carbon nanotube-based composite material is used as the cavity transmission layer, and the cavity transmission layer can be used as a film to be combined with organic and inorganic layers in a direct transferring or coating manner, so that cavity fetching and transmission effects are realized. The carbon nanotube-based composite material is used as the cavity transmission layer, so that the high-efficiency cavity transmission/electron interception effect is realized without the need of high-temperature quenching. The carbon nanotubes and the P type semiconductors are low in cost, abundant and nontoxic.
Description
Technical field
The present invention relates to a kind of novel solar battery device and preparation method thereof, belong to solar cell material field.
Background technology
Along with the development of material and highlighting of clean reproducible energy importance, novel optoelectronic materials is subject to paying close attention to more and more widely in the application of area of solar cell.The commercialization of monocrystaline silicon solar cell achieves solar cell moves towards market impressive progress from laboratory, has also driven further developing of area of solar cell greatly.But monocrystaline silicon solar cell efficiency is difficult to realize more quantum jump, the harshness of production procedure, and the very big dependence of HIGH-PURITY SILICON is all limited it further develop.In order to realize reducing costs further, improve battery efficiency, novel solar battery is constantly developed and develops, as polysilicon, and non-crystal silicon solar cell, multi-element compounds solar cell, sensitization solar battery, and organic solar batteries.Wherein organic solar batteries especially in recent years popular battery-perovskite solar cell be undoubtedly the developing star of solar cell.
As far back as 20 beginnings of the century, Pochettino and Volmer reports the photoconductive effect of organic solid-state anthracene crystal respectively, becomes the significant beginning of organic solar batteries research.Tang achieved the battery efficiency (C.W.Tang of 1% in 1979 with the heterojunction that two kinds of different organic dyestuff are made, USPatent4,164,431, August14,, and reported the breakthrough (C.W.Tang, Appl.Phys.Lett.48 (1986) 183.) in this organic solar batteries field in 1986 1979).Be separated and transmitting effect electron hole although people have understood heterostructure, organic solar batteries still cannot obtain desirable efficiency in considerable time.By continuous research, A.R.Schlatman finds that the indium ion in ito glass easily diffuses into organic active layer and catches charge carrier (A.R.Schlatman, Appl.Phys.Lett.69 (1996) 1764.), thus reduce the performance of device.Aluminium electrode also has the situation similar to ITO electrode, diffuses into organic active layer, thus affects the overall performance of device.Another major reason affecting battery efficiency is not mated at the interface that semiconductor contacts with metal electrode because of being with and forming the Schottky barrier hindering electric transmission.Although the 3rd reason generates electron hole pair by p-n junction, because internal electric field is little, or material is to reasons such as the selective power differences of electron hole, makes electrons spread reduce charge carrier to anode and electrode compound and exports.The main method tackling these problems just constructs a resilient coating (S.A.Carter, Appl.Phys.Lett.70 (1997) 2067.) between active layer and electrode.((poly (styrenesulfonate) (PEDOT-PSS) is a kind of conventional hole transmission layer to poly (3,4-ethylenedioxythiophene)) –.It can improve interface, tissue electrode ion diffuse, improves battery delivery efficiency.But its unsteadiness is difficult to solve always.M.D.Irwin nickel oxide is applied on organic solar batteries as hole transmission layer, in order to replace PEDOT-PSS and to obtain reasonable effect (M.D.Irwin, PNAS.105 (2007) 2783.), the energy gap of simultaneous oxidation nickel is large, the interception to electronics can be realized, reduce electronics in the loss of anode compound, to improved efficiency, there is positive effect.But also just because of the bandwidth ratio of nickel oxide is comparatively large, its conductive effect is poor.Also have other hole transmission layer a lot of studied with report, but be difficult to balance between stability and conductivity.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of novel solar battery device and preparation method thereof is provided, the present invention is using carbon nano-tube based composites as hole transmission layer, carbon nano-tube based composites hole transmission layer has high stability, environmental friendliness etc., raw material are sufficient and easily obtain feature.
Object of the present invention can be achieved through the following technical solutions:
A kind of novel solar battery device, comprises anode, hole transmission layer, active layer, electron transfer layer, transparency electrode and substrate that order stratiform is laid,
Described hole transmission layer is: the Rotating fields be mixed into by carbon nano-tube and P type semiconductor, or the double-layer structure be made up of independent carbon nanotube layer and p type semiconductor layer.Namely hole transmission layer of the present invention is the composite material adopting carbon nano-tube and P type semiconductor, hereinafter referred to as carbon nano-tube based composites.
When described hole transmission layer is the Rotating fields be mixed into by carbon nano-tube and P type semiconductor, now described thickness of hole transport layer is between 2-500 nanometer, and carbon nano-tube and P type semiconductor weight ratio are between 1:100 and 100:1.
When described hole transmission layer is the double-layer structure be made up of independent carbon nanotube layer and p type semiconductor layer, the thickness of described carbon nanotube layer is 1-200 nanometer, and described P type semiconductor layer thickness is 0.5-300 nanometer.
When described hole transmission layer is the double-layer structure be made up of independent carbon nanotube layer and p type semiconductor layer, the setting position of carbon nanotube layer and p type semiconductor layer can adopt following three kinds of modes:
A, described carbon nanotube layer are connected with active layer, and described p type semiconductor layer is connected with anode, or,
B, described carbon nanotube layer are connected with anode, and described p type semiconductor layer is connected with active layer, or,
C, described novel solar battery device comprise anode, electron transfer layer, active layer, carbon nanotube layer, p type semiconductor layer, transparency electrode and the substrate that order stratiform is laid.B, c two kinds of forms are the inverted situation of hole transmission layer.
Described carbon nano-tube is selected from one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes, and the diameter of described carbon nano-tube is 0.4-20 nanometer.
Described P type semiconductor is selected from one or more in P type graphene quantum dot, P type graphene oxide, P type nickel oxide or P type vanadic oxide; Described P type semiconductor bandwidth is 2.0-4.5 electron-volt.
Described transparency electrode is indium tin oxide ITO electrode or FTO electrode, described substrate is glass, described active layer material is selected from methylamino lead iodide, poly (3-hexylthiophene) (i.e. P3HT) or PCBM ([6,6]-phenyl-C61-butyricacidmethylester), described electron transport layer materials is selected from zinc oxide or titanium oxide, and described anode material is selected from silver, aluminium or material with carbon element.
Described hole transmission layer is directly connected with between anode, or by arranging protective layer between hole transmission layer with anode, hole transmission layer is connected indirectly with anode.
The Material selec-tion PMMA etc. of described protective layer.
The preparation method of above-mentioned novel solar battery device, comprises the following steps:
1) transparency electrode is arranged on substrate, and cleans up, dry up, then use oxygen plasma treatment two minutes;
2) one deck dense film is formed by thermal decomposition on transparency electrode surface, then mesopore film is formed by spin-coating method, the electron transfer layer (material preparing dense film or mesopore film is zinc oxide or titanium oxide) described in dense film and mesopore film form on dense film surface;
3) active layer is formed by spin-coating method on electron transfer layer surface;
4) by impression mode or spin coating mode, carbon nano-tube film is transferred to active layer surface, spin coating forms p type semiconductor layer, forms hole transmission layer, or,
After carbon nano-tube is mixed with P type semiconductor, to impress or carbon nano-tube and P type semiconductor mixture are formed hole transmission layer on active layer surface by spin coating mode;
5) on hole transmission layer, form protective layer by spin-coating method, be finally connected with anode, or, direct jointed anode on hole transmission layer.
In above-mentioned preparation method, the thickness of layers of material can pass through the concentration of this material, and rotary speed controls.
The carbon nano-tube based composites that P type semiconductor is formed in conjunction with carbon nano-tube has the charge carrier high rate of dissociation as hole transmission layer, high conductivity, electronic blocking, and modifying interface reduces the performances such as potential energy barrier.Carbon nano-tube has high conductivity and carrier mobility, and the P type semiconductor simultaneously in broadband range of the present invention promotes the electric conductivity of carbon nano-tube further to the modification of carbon nano-tube and doping.Carbon nano-tube has strong dissociation capability to electron hole pair, realizes the efficient effect with transmission that is separated.P type semiconductor realizes, to the effect of electronics interception, affecting device performance to prevent electronics and hole in anode compound as electronic barrier layer.P type semiconductor simultaneously can carbon nano-tube modified and electrode, reduces carbon nano-tube and interelectrode potential energy barrier, the open circuit voltage of raising device.And carbon nano-tube based composites hole transmission layer can realize inverted structure (namely above-mentioned b, c two kinds of forms) as required in solar cells.So, when the carbon nano-tube based composites formed in conjunction with carbon nano-tube with P type semiconductor is as hole transmission layer, hole concentration and transmission rate can be improved, reduce the loss of charge carrier on electrode simultaneously, to the current efficiency and power improving device, there is very important effect.Make the selection of device to other active layer material and electrode material have flexibility simultaneously, promote that its organic solar batteries to different structure, different materials is unified and realize hole transport, the effect of electronics interception.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, the carbon nano-tube based composites that the present invention is used directly can shift in the mode of film as hole transmission layer or coating method realizes being combined with organic-inorganic layer, reaches hole and takes out, the effect of transmission.
2, the carbon nano-tube based composites that the present invention is used does not need quench hot can realize the effect of efficient hole transport/electronics interception as hole transmission layer.
3, the carbon nano-tube that the present invention is used and P type semiconductor material cheapness are abundant, nontoxic.
Accompanying drawing explanation
Fig. 1 is the structural representation of solar cell device in embodiment 1;
Fig. 2 is the structural representation of solar cell device in embodiment 12;
Fig. 3 is the structural representation of solar cell device in embodiment 13;
Fig. 4 is the current density-voltage characteristic figure of solar cell device in embodiment 13.
Number in the figure, 1 is carbon nanotube layer, and 2 is p type semiconductor layer, and 3 is substrate, and 4 is transparency electrode, and 5 is active layer, and 6 is electron transfer layer, and 7 is anode.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The P type semiconductor materials such as transparency electrode (FTO, ITO) used, active layer material, carbon nano-tube, vanadic oxide, and metal electrode etc. is commercial product.
A kind of novel solar battery device, as shown in Figure 1, comprise anode 7, p type semiconductor layer 2, carbon nanotube layer 1, active layer 5, electron transfer layer 6, transparency electrode 4 and substrate 3 that order stratiform is laid, wherein, p type semiconductor layer 2 and carbon nanotube layer 1 form hole transmission layer.Namely hole transmission layer is the composite material adopting carbon nano-tube and P type semiconductor, hereinafter referred to as carbon nano-tube based composites.
The thickness of carbon nanotube layer 1 is 10 nanometers, and p type semiconductor layer 2 thickness is 0.5-300 nanometer.
In the present embodiment, carbon nano-tube is selected from Single Walled Carbon Nanotube, and its diameter is 0.4-20 nanometer.P type semiconductor is selected from P type graphene oxide; P type semiconductor bandwidth is 2.0-4.5 electron-volt.Transparency electrode is FTO electrode, and substrate is glass, and active layer material is selected from methylamino lead iodide, and electron transport layer materials is selected from titanium oxide, and anode material is selected from silver, aluminium or material with carbon element.
The preparation method of above-mentioned novel solar battery device, comprises the following steps:
1) transparency electrode is arranged on substrate, and cleans up, dry up, then use oxygen plasma treatment two minutes; 2) formed the titanium deoxid film of one deck densification on transparency electrode surface by thermal decomposition, then form mesoporous titanium dioxide film on dense film surface by spin-coating method, dense film and mesopore film form electron transfer layer; 3) by spin-coating method at electron transfer layer surface spin coating lead iodide solution, anneal 30 minutes, then forms methylamino lead iodide active layer in immersion methylpyridinium iodide ammonium; 4) the single armed carbon nano-tube being 10 nanometers by thickness by impression mode or spin coating mode is combined with this active layer by direct transfer process, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize P type semiconductor material to be also directly connected with active layer with the composite construction of carbon nano-tube, form hole transmission layer.5) at hole transmission layer plated surface Anodic.
In above-mentioned preparation method, the thickness of layers of material can pass through the concentration of this material, and rotary speed controls.
Embodiment 2
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 50 nanometers is combined with active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 3
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 200 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 4
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the both arms carbon nano-tube of 10 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 5
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the both arms carbon nano-tube of 10 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 6
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by spin-coating method by thickness, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 7
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by spin-coating method by thickness, then at the nano oxidized alkene of carbon nano tube surface spin coating 150, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 8
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by spin-coating method by thickness, then at the nano oxidized alkene of carbon nano tube surface spin coating 5, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 9
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 0.5 nano-graphene quantum dot, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 10
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 5 nano-nickel oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 11
A kind of novel solar battery device, structure as shown in Figure 1.Preparation method is: FTO glass cleaning is clean, dries up, then uses oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 5 nano-nickel oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 12
A kind of novel solar battery device, structure as shown in Figure 2, comprise anode 7, electron transfer layer 6, active layer 5, carbon nanotube layer 1, p type semiconductor layer 2, transparency electrode 4 and substrate 3 that order stratiform is laid, wherein, p type semiconductor layer 2 and carbon nanotube layer 1 form hole transmission layer.Namely hole transmission layer is the composite material adopting carbon nano-tube and P type semiconductor, hereinafter referred to as carbon nano-tube based composites.
The thickness of carbon nanotube layer 1 is 3 nanometers, and p type semiconductor layer 2 thickness is 0.5-300 nanometer.
In the present embodiment, carbon nano-tube is selected from Single Walled Carbon Nanotube, and its diameter is 0.4-20 nanometer.P type semiconductor is selected from P type vanadic oxide; P type semiconductor bandwidth is 2.0-4.5 electron-volt.Transparency electrode is ITO electrode, and substrate is glass, and active layer material is selected from PCBM, and electron transport layer materials is selected from zinc oxide, and anode material is selected from silver, aluminium or material with carbon element.
Preparation method is: cleaned up by ito glass, dries up, and then uses oxygen plasma treatment two minutes.At the vanadic oxide of ITO surface spin coating 2nm, the then carbon nano-tube of spin coating 3 nanometer, realizes P type semiconductor material and is also directly connected with active layer with the composite construction of carbon nano-tube.Then at carbon nano tube surface spin coating PCBM as active layer, then at active layer surface spin coating electron transfer layer, then plate electrode.
Embodiment 13
A kind of novel solar battery device, structure as shown in Figure 3, is the inverted situation of hole transmission layer, comprises anode 7, carbon nanotube layer 1, p type semiconductor layer 2, active layer 5, electron transfer layer 6, transparency electrode 4 and substrate 3 that order stratiform is laid.
Preparation method is:
FTO glass cleaning is clean, dry up, then use oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that 0.5 nano graphene oxide is combined with this active layer by spin-coating method by thickness, then shift the single armed carbon nano-tube of 10 nanometers at surface of graphene oxide direct transfer process, realize P type semiconductor material and be also directly connected with active layer with the composite construction of carbon nano-tube.Electrode is plated subsequently in surface of graphene oxide.
As shown in Figure 4, graphene oxide is used as electronic barrier layer to reduce the loss of electron hole in anode compound to improve the efficiency of battery to the current density-voltage response of the novel solar battery device that the present embodiment obtains.The photoelectric conversion efficiency of battery can be calculated by current density-voltage response.
Embodiment 14
FTO glass cleaning is clean, dry up, then use oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Single armed carbon nano-tube and graphene oxide are mixed by 100:5 the composite construction that realizes P type semiconductor material and carbon nano-tube and is formed the composite hole transporting layer of 10 nanometers by spin-coating method on active layer surface.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 15
FTO glass cleaning is clean, dry up, then use oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Single armed carbon nano-tube is mixed by 20:1 with graphene oxide, realizes the composite construction of P type semiconductor material and carbon nano-tube and form the composite hole transporting layer of 10 nanometers by spin-coating method on active layer surface.Electrode is plated subsequently in surface of graphene oxide.
Embodiment 16
FTO glass cleaning is clean, dry up, then use oxygen plasma treatment two minutes.Formed the titanium deoxid film of one deck densification at glass surface by thermal decomposition, then mesoporous titanium dioxide film is formed on compacted zone surface by spin-coating method, at titanium dioxide surface spin coating lead iodide solution, anneal 30 minutes, then immerse in methylpyridinium iodide ammonium and form methylamino lead iodide active layer.Be that the single armed carbon nano-tube of 10 nanometers is combined with this active layer by direct transfer process by thickness, then at carbon nano tube surface spin coating 0.5 nano graphene oxide, realize the composite construction of P type semiconductor material and carbon nano-tube and be directly connected with active layer.Then at the PMMA of composite hole transporting layer surface spin coating 100 nanometer, electrode is plated subsequently.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a novel solar battery device, is characterized in that, comprises anode, hole transmission layer, active layer, electron transfer layer, transparency electrode and substrate that order stratiform is laid,
Described hole transmission layer is: the Rotating fields be mixed into by carbon nano-tube and P type semiconductor, or the double-layer structure be made up of independent carbon nanotube layer and p type semiconductor layer.
2. a kind of novel solar battery device according to claim 1, it is characterized in that, when described hole transmission layer is the Rotating fields be mixed into by carbon nano-tube and P type semiconductor, now described thickness of hole transport layer is between 2-500 nanometer, and carbon nano-tube and P type semiconductor weight ratio are between 1:100 and 100:1.
3. a kind of novel solar battery device according to claim 1, it is characterized in that, when described hole transmission layer is the double-layer structure be made up of independent carbon nanotube layer and p type semiconductor layer, the thickness of described carbon nanotube layer is 1-200 nanometer, and described P type semiconductor layer thickness is 0.5-300 nanometer.
4. a kind of novel solar battery device according to claim 3, it is characterized in that, described carbon nanotube layer is connected with active layer, and described p type semiconductor layer is connected with anode, or,
Described carbon nanotube layer is connected with anode, and described p type semiconductor layer is connected with active layer, or,
Described novel solar battery device comprises anode, electron transfer layer, active layer, carbon nanotube layer, p type semiconductor layer, transparency electrode and the substrate that order stratiform is laid.
5. a kind of novel solar battery device according to claim 1, it is characterized in that, described carbon nano-tube is selected from one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes, and the diameter of described carbon nano-tube is 0.4-20 nanometer.
6. a kind of novel solar battery device according to claim 1, is characterized in that, described P type semiconductor is selected from one or more in P type graphene quantum dot, P type graphene oxide, P type nickel oxide or P type vanadic oxide; Described P type semiconductor bandwidth is 2.0-4.5 electron-volt.
7. a kind of novel solar battery device according to claim 1, it is characterized in that, described transparency electrode is indium tin oxide ITO electrode or FTO electrode, described substrate is glass, described active layer material is selected from methylamino lead iodide, P3HT or PCBM, described electron transport layer materials is selected from zinc oxide or titanium oxide, and described anode material is selected from silver, aluminium or material with carbon element.
8. a kind of novel solar battery device according to claim 1, it is characterized in that, described hole transmission layer is directly connected with between anode, or by arranging protective layer between hole transmission layer with anode, hole transmission layer is connected indirectly with anode.
9. a kind of novel solar battery device according to claim 7, is characterized in that, the Material selec-tion PMMA of described protective layer.
10. a preparation method for novel solar battery device as claimed in claim 1, is characterized in that, comprise the following steps:
1) transparency electrode is arranged on substrate, and cleans up, dry up, then use oxygen plasma treatment two minutes;
2) form one deck dense film by thermal decomposition on transparency electrode surface, then form mesopore film by spin-coating method, the electron transfer layer described in dense film and mesopore film form on dense film surface;
3) active layer is formed by spin-coating method on electron transfer layer surface;
4) by impression mode or spin coating mode, carbon nano-tube film is transferred to active layer surface, spin coating forms p type semiconductor layer, forms hole transmission layer, or,
After carbon nano-tube is mixed with P type semiconductor, to impress or carbon nano-tube and P type semiconductor mixture are formed hole transmission layer on active layer surface by spin coating mode;
5) on hole transmission layer, form protective layer by spin-coating method, be finally connected with anode, or, direct jointed anode on hole transmission layer.
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| CN110233203A (en) * | 2018-03-06 | 2019-09-13 | 江苏理工学院 | A kind of class superlattices Zn-Sb/Ge-Sb nano phase change memory films and preparation method thereof for worst hot case |
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| CN111384267A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Preparation method of graphene quantum dot film, light-emitting diode and preparation method of light-emitting diode |
| CN111384267B (en) * | 2018-12-29 | 2021-09-10 | Tcl科技集团股份有限公司 | Preparation method of graphene quantum dot film, light-emitting diode and preparation method of light-emitting diode |
| WO2022249648A1 (en) * | 2021-05-24 | 2022-12-01 | パナソニックホールディングス株式会社 | Composition and method for producing electronic device using same |
| CN114093955A (en) * | 2021-10-15 | 2022-02-25 | 华南理工大学 | Gallium arsenide solar cell with carbon nanofiber doped with nickel oxide hole transport layer and preparation method thereof |
| CN114093955B (en) * | 2021-10-15 | 2024-03-08 | 华南理工大学 | Gallium arsenide solar cell with carbon nanofiber doped with nickel oxide hole transport layer and preparation method of gallium arsenide solar cell |
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