CN102810575A - Solar energy battery device and preparation method thereof - Google Patents
Solar energy battery device and preparation method thereof Download PDFInfo
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- CN102810575A CN102810575A CN2011101497520A CN201110149752A CN102810575A CN 102810575 A CN102810575 A CN 102810575A CN 2011101497520 A CN2011101497520 A CN 2011101497520A CN 201110149752 A CN201110149752 A CN 201110149752A CN 102810575 A CN102810575 A CN 102810575A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 116
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims description 96
- 239000011248 coating agent Substances 0.000 claims description 94
- 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 44
- 238000007740 vapor deposition Methods 0.000 claims description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 18
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- 229920000109 alkoxy-substituted poly(p-phenylene vinylene) Polymers 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005083 Zinc sulfide Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 7
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 7
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- -1 3-aminomethyl phenyl Chemical group 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- LWGKBODJSZZWHB-UHFFFAOYSA-N ethene thiophene Chemical compound S1C=CC=C1.C=C.C=C LWGKBODJSZZWHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229920000553 poly(phenylenevinylene) Polymers 0.000 claims description 2
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000003139 buffering effect Effects 0.000 abstract 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 39
- 238000004528 spin coating Methods 0.000 description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 229920000144 PEDOT:PSS Polymers 0.000 description 24
- 238000010276 construction Methods 0.000 description 15
- 239000003599 detergent Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 238000009504 vacuum film coating Methods 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 229920000264 poly(3',7'-dimethyloctyloxy phenylene vinylene) Polymers 0.000 description 9
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QHODXIVESWMRGP-UHFFFAOYSA-N NCC=1C=C(C=CC1)C1=C(C=CC(=C1)NC1=CC=CC=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 Chemical compound NCC=1C=C(C=CC1)C1=C(C=CC(=C1)NC1=CC=CC=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 QHODXIVESWMRGP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical class CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Images
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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
- 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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- Photovoltaic Devices (AREA)
Abstract
The invention relates to a solar energy battery device. The solar energy battery device comprises a substrate, a cathode, an electron buffering layer, an active layer, an electron hole buffering layer and an anode which are stacked sequentially, wherein the cathode is made of metal; and the anode comprises a first anode buffer layer, a metal layer and a second anode buffer layer which are stacked sequentially. The material of the first anode buffer layer and that of the second anode buffer layer are both chosen from small organic molecules or sulfides. The solar energy battery device has high efficiency in energy conversion. In addition, the invention further provides a preparation method for the solar energy battery device.
Description
[technical field]
The present invention relates to a kind of solar cell device and preparation method thereof, especially relate to solar cell device of a kind of inverted structure and preparation method thereof.
[background technology]
Solar cell device owing to have cheapness, cleaning, advantage such as renewable has obtained using widely.Traditional solar cell device generally includes the ito anode/hole resilient coating/active layer/electron buffer layer/negative electrode that stacks gradually at present.During use, light is incident to solar cell from ito anode, and light is in ito anode one side incident, and substrate of glass can absorb and reflecting part light, thereby the energy conversion efficiency of this solar cell device is lower.
[summary of the invention]
Based on this, be necessary to provide a kind of energy conversion efficiency higher solar energy battery device.
A kind of solar cell device; Comprise the substrate, negative electrode, electron buffer layer, active layer, hole resilient coating and the anode that stack gradually; Negative electrode is a metallic cathode; Anode comprises first anode resilient coating, metal level and the second plate resilient coating that stacks gradually, and wherein the material of first anode resilient coating and second plate resilient coating all is selected from a kind of in organic molecule and the sulfide.
In a preferred embodiment, negative electrode is selected from a kind of in aluminium, silver, calcium, gold and the platinum.
In a preferred embodiment, the material of first anode resilient coating and second plate resilient coating is selected from N, N '-two (3-aminomethyl phenyl)-N; N '-diphenyl-4,4 '-benzidine, oxine aluminium, CuPc and 2,9-dimethyl-4; 7-diphenyl-1, a kind of in the 10-phenanthroline.
In a preferred embodiment, the material of first anode resilient coating and second plate resilient coating is selected from a kind of in zinc sulphide, manganese sulfide, vulcanized lead and the cadmium sulfide.
In a preferred embodiment, the material of metal level is selected from a kind of in aluminium, silver, calcium, platinum and the gold.
In a preferred embodiment, the material of electron buffer layer is selected from a kind of in lithium fluoride, lithium carbonate, cesium carbonate, nitrogenize caesium, cesium fluoride, cesium chloride, cesium iodide and the cesium bromide.
In a preferred embodiment, the material of active layer is selected from a kind of among P3HT:PCBM, MODO-PPV:PCBM and the MEH-PPV:PCBM.
In a preferred embodiment, the material of hole resilient coating is for gathering 3, the mixture of 4-dioxy ethene thiophene and polyphenyl sodium sulfonate.
In a preferred embodiment, substrate is a substrate of glass.
In addition, also be necessary to provide a kind of preparation method of energy conversion efficiency higher solar energy battery device.
A kind of preparation method of solar cell device may further comprise the steps: step 1, a substrate is provided; Step 2, in substrate, form negative electrode, negative electrode is a metallic cathode; Step 3, the electron buffer layer that on negative electrode, forms; Step 4, on electron buffer layer, form active layer; Step 5, on active layer, form the hole resilient coating; And step 6, on the resilient coating of hole vapor deposition first anode resilient coating; Follow vapor deposition layer of metal layer; Vapor deposition second plate resilient coating is forming anode on metal level again, and the material of first anode resilient coating and second plate resilient coating all is selected from a kind of in organic molecule and the sulfide.
Above-mentioned solar cell device and manufacturing approach thereof, negative electrode are between substrate and electron buffer layer, and anode is an incidence surface; Light avoids light from substrate one side incident from anode one side incident, can avoid substrate absorption and reflection ray; The refractive index of micromolecule and sulfide is big (being generally more than 2.0), can most light be incided in the active layer of device, improves the absorptivity of light; The source is simple simultaneously, and is cheap, and little to the injection and the transmission influence in hole; Can reduce injection barrier to a certain extent, help the hole and arrive anode, thereby improve the energy conversion efficiency of solar cell device.
[description of drawings]
Through the more specifically explanation of the preferred embodiments of the present invention shown in the accompanying drawing, above-mentioned and other purpose, characteristic and advantage of the present invention will be more clear.Reference numeral identical in whole accompanying drawings is indicated identical part.Painstakingly do not draw accompanying drawing, focus on illustrating purport of the present invention by actual size equal proportion convergent-divergent.
Fig. 1 is the structural representation of the solar cell device of an embodiment;
Fig. 2 is preparation method's the flow chart of the solar cell device of an embodiment;
Fig. 3 is the current density and the voltage relationship figure of the solar cell device of embodiment one.
[embodiment]
For make above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, does detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.A lot of details have been set forth in the following description so that make much of the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention does not receive the restriction of following disclosed practical implementation.
See also Fig. 1, an embodiment solar cell device 100 comprises and stacks gradually substrate 10, negative electrode 20, electron buffer layer 30, active layer 40, hole resilient coating 50 and anode 60.
Negative electrode 20 is formed at substrate 10 surfaces.Negative electrode 20 is a metallic cathode.The material of negative electrode 20 is selected from a kind of in aluminium (Al), silver (Ag), calcium (Ca), gold (Au) and the platinum (Pt).
Electron buffer layer 30 is formed at negative electrode 20 surfaces.The material of electron buffer layer 30 is selected from lithium fluoride (LiF), lithium carbonate (Li
2CO
3), cesium carbonate (Cs
2CO
3), nitrogenize caesium (CsN
3), a kind of in cesium fluoride (CsF), cesium chloride (CsCl), cesium iodide (CsI) and the cesium bromide (CsBr).
Active layer 40 is formed at electron buffer layer 30 surfaces.The material of active layer 40 is selected from P3HT (gathering the 3-hexyl thiophene): PCBM (the methyl butyrate derivative of fullerene), MDMO-PPV (gathering 2-methoxyl group-5-(3,7-dimethyl octyloxy) phenylenevinylene): PCBM and MEH-PPV (gather [2-methoxyl group-5-(2 '-vinyl-own oxygen base) gathers the styrene support): a kind of among the PCBM.
Hole resilient coating 50 is formed at active layer 40 surfaces.Hole resilient coating 50 is for gathering 3, the mixture of 4-dioxy ethene thiophene (PEDOT) and polyphenyl sodium sulfonate (PSS).
Anode 60 is formed at hole resilient coating 50 surfaces.Negative electrode 60 is a stepped construction, comprises the first anode resilient coating 61, metal level 63 and the second plate resilient coating 65 that stack gradually.The material of first anode resilient coating 61 and second plate resilient coating is selected from a kind of in organic molecule and the sulfide, and organic molecule is selected from N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium (Alq
3), CuPc (CuPc) and 2,9-dimethyl-4,7-diphenyl-1, a kind of in the 10-phenanthroline (BCP), sulfide is selected from a kind of in zinc sulphide (ZnS), manganese sulfide (MnS), vulcanized lead (PbS) and the cadmium sulfide (CdS).The material of metal level 63 be preferably have high conductivity, the metal of high permeability, the material of metal level 63 is for being selected from a kind of in aluminium (Al), silver (Ag), calcium (Ca), platinum (Pt) and the gold (Au).Be appreciated that the material of first anode resilient coating 61 and second plate resilient coating 65 can be identical also can be inequality.
In this solar cell device 100, negative electrode 20 is not exposed in the air between substrate 10 and electron buffer layer 30, can prevent effectively that negative electrode 20 and airborne oxygen from reacting, thereby has improved the stability of solar cell device 100.Simultaneously, when this solar cell device 100 used, anode 60 was an incidence surface, and light avoids light from substrate 10 1 side incidents from anode 60 1 side incidents, can avoid substrate 10 absorptions and reflection ray, has improved the energy conversion efficiency of solar cell device 100.Anode 60 is a stepped construction in the solar cell device 100, and the material of first anode resilient coating 61 and second plate resilient coating 65 is organic molecule or sulfide, and the refractive index of micromolecule and sulfide is big (being generally more than 2.0); Can most light be incided in the active layer of device; Improve the absorptivity of light, the source is simple simultaneously, and is cheap; And it is little to the injection and the transmission influence in hole; Can reduce injection barrier to a certain extent, help the hole and arrive anode, thereby the photoelectric conversion efficiency of this solar cell device 100 be higher.
Please consult Fig. 2 simultaneously, the preparation method of the solar cell device 100 of an embodiment, it may further comprise the steps:
Step S110, a substrate 10 is provided, and removes the organic pollution on substrate 10 surfaces.This conductive substrates 10 is a glass.Substrate 10 adopts liquid detergent, ethanol, acetone and pure water to clean to remove the organic pollution on substrate 10 surfaces.
Step S120, in substrate 10, form negative electrode 20.Negative electrode 20 is a metallic cathode.Negative electrode 20 is formed by vapor deposition, and thickness is 20～200nm.The material of negative electrode 20 is selected from a kind of in aluminium (Al), silver (Ag), calcium (Ca), gold (Au) and the platinum (Pt).
Step S130, form electron buffer layer 30 on negative electrode 20 surface.Electron buffer layer 30 is formed by vapor deposition, and thickness is 0.5～10nm.The material of electron buffer layer 30 is selected from lithium fluoride (LiF), lithium carbonate (Li
2CO
3), cesium carbonate (Cs
2CO
3), nitrogenize caesium (CsN
3), a kind of in the cesium fluoride (CsF), cesium chloride (CsCl).
Step S140, form active layers 40 on electron buffer layer 30 surface.Active layer 40 is spin-coated on electron buffer layer 30 surfaces by active layer solution and processes, and thickness is 80～300nm.The mass concentration of active layer material is 8～30mg/ml in the active layer solution; Solvent is selected from least a in toluene, xylenes, chlorobenzene and the chloroform; Active layer material is selected from a kind of among P3HT:PCBM, MDMO-PPV:PCBM and the MEH-PPV:PCBM; The quality of P3HT: PCBM is 0.8: 1-1: 1, and the mass ratio of MDMO-PPV: PCBM is 1: 1～1: 4, the mass ratio of MEH-PPV: PCBM is 1: 1-1: 4.During spin coating, in being full of the glove box of inert gas, carry out, annealed 10～100 minutes down at 50～200 ℃ afterwards, or at room temperature placed 24～48 hours.Wherein, active layer solution is preferably the P3HT:PCBM chlorobenzene solution that mass concentration is 24mg/ml, is preferably 150 ℃ of annealing 15min down, and the thickness of the active layer 40 of formation is preferably 120nm.
Step S150, form hole resilient coatings 50 on active layer 40 surface.Hole resilient coating 50 is spin-coated on active layer 40 surfaces by the aqueous solution of PEDOT:PSS and processes, and thickness is 20～80nm.The mass ratio of PEDOT and PSS is 2: 1～6: 1, and the mass concentration of PEDOT:PSS is 1%～5%.Heated 15～60 minutes down at 100～200 ℃ after the spin coating.Wherein, the mass concentration of PEDOT:PSS is preferably 1.3%, preferably heats 30 minutes down at 200 ℃ after the spin coating, and the thickness of the hole resilient coating 50 of formation is preferably 40nm.
Step S160, on this hole resilient coating 50 anode 60 of cambium layer stack structure.Resilient coating 50 surperficial vapor deposition first anode resilient coatings 61 at first in the hole, the thickness of first anode resilient coating 61 is 10～100nm; Follow vapor deposition layer of metal layer 63 on first anode resilient coating 61, the thickness of metal level 63 is 5～20nm; Vapor deposition second plate resilient coating 65 on metal level 63 at last, the thickness of second plate resilient coating 65 is 10～100nm.The material of first anode resilient coating 61 and second plate resilient coating all is selected from a kind of in organic molecule and the sulfide, and organic molecule is selected from N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine, oxine aluminium (Alq
3), CuPc (CuPc) and 2,9-dimethyl-4,7-diphenyl-1, a kind of in the 10-phenanthroline (BCP), sulfide is selected from a kind of in zinc sulphide (ZnS), manganese sulfide (MnS), vulcanized lead (PbS) and the cadmium sulfide (CdS).The material of metal level 63 be preferably have high conductivity, the metal of high permeability, the material of metal level 63 is for being selected from a kind of in aluminium (Al), silver (Ag), calcium (Ca), platinum (Pt) and the gold (Au).The material that is appreciated that first anode resilient coating 61 and second plate resilient coating 65 can be the same or different.
Above-mentioned solar cell device preparation method; Negative electrode 20 is arranged between substrate 10 and the electron buffer layer 30; Be not exposed in the air, can prevent effectively that negative electrode 20 and airborne oxygen from reacting, thereby can improve the stability of the solar cell device 100 of preparation.
Preparation method to solar cell device provided by the invention is elaborated below in conjunction with specific embodiment.
Embodiment one
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and cathode material is Al; Thickness is 150nm, follows the vapor deposition electron buffer layer, and material is LiF, and thickness is 0.7nm; Follow the spin coating active layer, material is P3HT:PCBM, and concentration is 24mg/ml, and the mass ratio of P3HT: PCBM is 0.8: 1; Solvent is a chloroform, and at 50 ℃ of 100min that anneal down, the thickness of active layer is 120nm, then spin coating hole resilient coating; Material is PEDOT:PSS, and the mass ratio of PEDOT: PSS is 4: 1, heats 30min down at 200 ℃, and the hole buffer layer thickness is 40nm; The anode that last vapor deposition has stepped construction, the material of first anode resilient coating is TPD, thickness is 60nm; The material of metal level is Ag, and thickness is 5nm, and the material of second plate resilient coating is TPD; Thickness is 80nm, obtains required polymer solar cell device at last.
See also Fig. 3, the structure that is depicted as preparation among the embodiment 1 is that solar cell device and the traditional structure of substrate/Al/LiF/P3HT:PCBM/PEDOT:PSS/ (TPD/Ag/TPD) is the current density and the voltage relationship of ITO substrate/PEDOT:PSS/P3HT:PCBM/LiF/Al solar cell device.
Can see that from Fig. 3 the current density of traditional solar cell device is 7.44mA/cm
2, and a kind of current density with solar cell device of inverted structure of embodiment has been brought up to 8.36mA/cm
2, this explanation, the solar cell device of inverted structure; There is more light to incide active layer,, makes the energy conversion efficiency of solar cell device obtain enhancing by the active layer utilization; The energy conversion efficiency of LiF implanted layer is 1.68%, and the energy conversion efficiency of inverted structure is 2%.
Embodiment two
Liquid detergent is used in substrate successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol; Remove the organic pollution of glass surface, put the vacuum film coating chamber the inside after handling into and carry out the vacuum moulding machine negative electrode, cathode material is Al, and thickness is 150nm; Follow the vapor deposition electron buffer layer, material is LiF, and thickness is 0.7nm, then the spin coating active layer; Material is P3HT:PCBM, and concentration is 8mg/ml, and the mass ratio of P3HT: PCBM is 1: 1, and solvent is a chloroform; At 50 ℃ of following annealing 100min, the thickness of active layer is 80nm, spin coating hole resilient coating then, and material is PEDOT:PSS; The mass ratio of PEDOT: PSS is 2: 1, and mass fraction is 1%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 80nm; The anode that last vapor deposition has stepped construction, the material of first anode resilient coating is TPD, and thickness is 40nm, and the material of metal level is Ag, and thickness is 10nm, and the material of second plate resilient coating is TPD, and thickness is 60nm, obtains required solar cell device at last.
Embodiment three
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and cathode material is Al; Thickness is 150nm, follows the vapor deposition electron buffer layer, and material is LiF, and thickness is 0.7nm; Follow the spin coating active layer, material is P3HT:PCBM, and concentration is 28mg/ml, P3HT: the PCBM mass ratio is 1: 1; Solvent is a chloroform, and at 150 ℃ of 5min that anneal down, active layer thickness is 160nm, then spin coating hole resilient coating; Material is that the mass ratio of PEDOT: PSS is 3: 1, and mass fraction is 5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 20nm; The anode that last vapor deposition has stepped construction, the material of ground floor D is TPD, thickness is 100nm; The material of metal level is Ag, and thickness is 20nm, and the material of second plate resilient coating is TPD; Thickness is 100nm, obtains required polymer solar cell device at last.
Embodiment four
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and cathode material is Ag; Thickness is 100nm, follows the vapor deposition electron buffer layer, and material is Cs
2CO
3, thickness is 10nm, follows the spin coating active layer, material is MEH-PPV:PCBM; Concentration is 12mg/ml, and the mass ratio of MEH-PPV: PCBM is 1: 4, and solvent is a chloroform, at 150 ℃ of 15min that anneal down; Active layer thickness is 300nm, spin coating hole resilient coating then, and material is PEDOT:PSS, the mass ratio of PEDOT: PSS is 4: 1; Mass fraction is 2.5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 50nm; The anode that last vapor deposition has stepped construction, first anode resilient coating be Alq
3, thickness is 100nm, and the material of metal level is Ag, and thickness is 15nm, and the material of second plate resilient coating is CuPc, thickness is 80nm, obtains required polymer solar cell device at last.
Embodiment five
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and cathode material is Ag; Thickness is 200nm, follows the vapor deposition electron buffer layer, and material is Cs
2CO
3, thickness is lnm, follows the spin coating active layer, material is MDMO-PPV:PCBM; Concentration is 20mg/ml, and the mass ratio of MDMO-PPV: PCBM is 1: 4, and solvent is a toluene, at room temperature places 48h; Active layer thickness is 200nm spin coating hole resilient coating then, and material is PEDOT:PSS, and the mass ratio of PEDOT: PSS is 3: 1; Mass fraction is 4.5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 70nm; The anode that last vapor deposition has stepped construction, the material of first anode resilient coating is BCP, thickness is 100nm; The material of metal level is Al, and thickness is 15nm, and the material of second plate resilient coating is BCP; Thickness is 80nm, obtains required polymer solar cell device at last.
Embodiment six
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and the material of negative electrode is Ca; Thickness is 50nm, follows the vapor deposition electron buffer layer, and material is Li
2CO
3, thickness is 5nm, follows the spin coating active layer, active layer material is P3HT:PCBM; Solvent is a chloroform, and concentration is 10mg/ml, and the mass ratio of P3HT: PCBM is 1: 1, at room temperature places 48h; Active layer thickness is 150nm spin coating hole resilient coating then, and material is PEDOT:PSS, and the mass ratio of PEDOT: PSS is 2: 1, and mass fraction is 4.5%; Heat 30min down at 200 ℃, the hole buffer layer thickness is 60nm, the anode that last vapor deposition has stepped construction, and the material of first anode resilient coating is Alq
3, thickness is 100nm, and the material of metal level is Al, and thickness is 15nm, and the material of second plate resilient coating is BCP, thickness is 80nm, obtains required polymer solar cell device at last.
Embodiment seven
Liquid detergent is used in substrate successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol; Remove the organic pollution of glass surface, put the vacuum film coating chamber the inside after handling into and carry out the vacuum moulding machine negative electrode, material is Au, and thickness is 90nm, then the vapor deposition electron buffer layer; Material is CsF, and thickness is 5nm, follows the spin coating active layer, and material is MEH-PPV:PCBM, and concentration is 10mg/ml; MEH-PPV: the PCBM mass ratio is 1: 4, and solvent is an xylenes, at room temperature places 48h, and active layer thickness is 220nm; Spin coating hole resilient coating then, material is PEDOT:PSS, PEDOT: the PSS mass ratio is 2: 1, mass fraction is 1.5%; Heat 30min down at 200 ℃, the hole buffer layer thickness is 45nm, the anode that last vapor deposition has stepped construction, and the material of first anode resilient coating is Alq
3, thickness is 20nm, and the material of metal level is Al, and thickness is 15nm, and the material of second plate resilient coating is BCP, thickness is 80nm, obtains required polymer solar cell device at last.
Embodiment eight
Liquid detergent is used in substrate successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol; Remove the organic pollution of glass surface, put the vacuum film coating chamber the inside after handling into and carry out the vacuum moulding machine negative electrode, the material of negative electrode is Ag, and thickness is 70nm, then the vapor deposition electron buffer layer; Material is CsF, and thickness is 5nm, follows the spin coating active layer, and material is MDMO-PPV:PCBM, and concentration is 16mg/ml; MDMO-PPV: the PCBM mass ratio is 1: 3, and solvent is a chlorobenzene, and at 200 ℃ of 5min that anneal down, active layer thickness is 250nm; Spin coating hole resilient coating then, material is PEDOT:PSS, PEDOT: the PSS mass ratio is 2: 1, mass fraction is 1.5%; Heat 30min down at 200 ℃, the hole buffer layer thickness is 30nm, the anode that last vapor deposition has stepped construction, and the material of first anode resilient coating is Alq
3, thickness is 100nm, and the material of metal level is Al, and thickness is 15nm, and the material of second plate resilient coating is Alq
3, thickness is 80nm, obtains required polymer solar cell device at last.
Embodiment nine
Liquid detergent is used in substrate successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol; Remove the organic pollution of glass surface, put the vacuum film coating chamber the inside after handling into and carry out the vacuum moulding machine negative electrode, the material of negative electrode is Ag, and thickness is 70nm, then the vapor deposition electron buffer layer; Material is CsF, and thickness is 5nm, follows the spin coating active layer, and material is P3HT:PCBM, and concentration is 8mg/ml; P3HT: the PCBM mass ratio is 1: 0.8, and solvent is a chlorobenzene, and at 200 ℃ of 25min that anneal down, active layer thickness is 100nm, then spin coating hole resilient coating; Material is PEDOT:PSS, and the mass ratio of PEDOT: PSS is 3: 1, and mass fraction is 3.5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 20nm; The anode that last vapor deposition has stepped construction, the material of first anode resilient coating is CdS, and thickness is 100nm, and the material of metal level is Au; Thickness is 10nm, and the material of second plate resilient coating is CuPc, and thickness is 80nm, obtains required polymer solar cell device at last.
Embodiment ten
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and the material of negative electrode is Ag; Thickness is 180nm, follows the vapor deposition electron buffer layer, and material is CsN
3, thickness is 7nm, follows the spin coating active layer, material is MDMO-PPV:PCBM; Concentration is 8mg/ml, MDMO-PPV: the PCBM mass ratio is 1: 1, and solvent is a chlorobenzene, at 100 ℃ of 30min that anneal down; Active layer thickness is 100nm, spin coating hole resilient coating then, and material is PEDOT:PSS, PEDOT: the PSS mass ratio is 4: 1; Mass fraction is 1.5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 35nm, the anode that last vapor deposition has stepped construction; The material of first anode resilient coating is ZnS, and thickness is 80nm, and the material of metal level is Ca, and thickness is 10nm; The material of second plate resilient coating is PbS, and thickness is 100nm, obtains required polymer solar cell device at last.
Embodiment 11
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and material is Ag; Thickness is 180nm, follows the vapor deposition electron buffer layer, and material is CsN
3, thickness is 7nm, follows the spin coating active layer, material is P3HT:PCBM; Concentration is 22mg/ml, P3HT: the PCBM mass ratio is 1: 1, and solvent is a chlorobenzene, at 70 ℃ of 100min that anneal down; Active layer thickness is 100nm, spin coating hole resilient coating then, and material is PEDOT:PSS, PEDOT: the PSS mass ratio is 5: 1; Mass fraction is 1.5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 55nm, the anode that last vapor deposition has stepped construction; The material of first anode resilient coating is ZnS, and thickness is 80nm, and the material of metal level is 10nm for Ca thickness; The material of second plate resilient coating is PbS, and thickness is 100nm, obtains required polymer solar cell device at last.
Liquid detergent, deionized water, acetone, ethanol are used in substrate successively; Each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface is put the vacuum film coating chamber the inside into and is carried out the vacuum moulding machine negative electrode after handling, and cathode material is Ag; Thickness is 180nm, follows the vapor deposition electron buffer layer, and material is CsN
3, thickness is 7nm, follows the spin coating active layer, material is P3HT:PCBM; Concentration is 26mg/ml, P3HT: the PCBM mass ratio is 1: 1, and solvent is a chlorobenzene, at 70 ℃ of 30min that anneal down; Active layer thickness is 120nm, spin coating hole resilient coating then, and material is PEDOT:PSS, PEDOT: the PSS mass ratio is 5: 1; Mass fraction is 1.5%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 60nm, the anode that last vapor deposition has stepped construction; The material of first anode resilient coating is MnS, and thickness is 80nm, and the material of metal level is Pt, and thickness is 100nm; The material of second plate resilient coating is PbS, and thickness is 100nm, obtains required polymer solar cell device at last.
Embodiment 13
Liquid detergent is used in substrate successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol; Remove the organic pollution of glass surface, put the vacuum film coating chamber the inside after handling into and carry out the vacuum moulding machine negative electrode, cathode material is Al, and thickness is 20nm, then the vapor deposition electron buffer layer; Material is CsCl, and thickness is 0.5nm, follows the spin coating active layer, and material is MEH-PPV:PCBM, and concentration is 28mg/ml; MEH-PPV: the PCBM mass ratio is 1: 2, and solvent is a chlorobenzene, and at 200 ℃ of 30min that anneal down, active layer thickness is 180nm, then spin coating hole resilient coating; Material is PEDOT:PSS, PEDOT: the PSS mass ratio is 5: 1, and mass fraction is 1.3%, heats 30min down at 200 ℃, and the hole buffer layer thickness is 70nm; The anode that last vapor deposition has stepped construction, the material of ground floor D is TPD, and thickness is 10nm, and the material of metal level is Pt; Thickness is 20nm, and the material of second plate resilient coating is TPD, and thickness is 10nm, obtains required polymer solar cell device at last.
The above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with accompanying claims.
Claims (10)
1. solar cell device; It is characterized in that: comprise the substrate, negative electrode, electron buffer layer, active layer, hole resilient coating and the anode that stack gradually; This negative electrode is a metallic cathode; This anode comprises first anode resilient coating, metal level and the second plate resilient coating that stacks gradually, and wherein the material of this first anode resilient coating and this second plate resilient coating all is selected from a kind of in organic molecule and the sulfide.
2. solar cell device according to claim 1 is characterized in that: this negative electrode is selected from a kind of in aluminium, silver, calcium, gold and the platinum.
3. solar cell device according to claim 1; It is characterized in that: the material of this first anode resilient coating and this second plate resilient coating is selected from N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4; 4 '-benzidine, oxine aluminium, CuPc and 2; 9-dimethyl-4,7-diphenyl-1, a kind of in the 10-phenanthroline.
4. solar cell device according to claim 1 is characterized in that: the material of this first anode resilient coating and this second plate resilient coating is selected from a kind of in zinc sulphide, manganese sulfide, vulcanized lead and the cadmium sulfide.
5. solar cell device according to claim 1 is characterized in that: the material of this metal level is selected from a kind of in aluminium, silver, calcium, platinum and the gold.
6. solar cell device according to claim 1 is characterized in that: the material of this electron buffer layer is selected from a kind of in lithium fluoride, lithium carbonate, cesium carbonate, nitrogenize caesium, cesium fluoride, cesium chloride, cesium iodide and the cesium bromide.
7. solar cell device according to claim 1 is characterized in that: the material of this active layer is selected from a kind of among P3HT:PCBM, MODO-PPV:PCBM and the MEH-PPV:PCBM.
8. solar cell device according to claim 1 is characterized in that: the material of this hole resilient coating is for gathering 3, the mixture of 4-dioxy ethene thiophene and polyphenyl sodium sulfonate.
9. solar cell device according to claim 1 is characterized in that: this substrate is a substrate of glass.
10. the preparation method of a solar cell device may further comprise the steps:
Step 1, a substrate is provided;
Step 2, in this substrate, form negative electrode, this negative electrode is a metallic cathode;
Step 3, on this negative electrode, form electron buffer layer;
Step 4, on this electron buffer layer, form active layer;
Step 5, on this active layer, form the hole resilient coating; And
Step 6, on this hole resilient coating vapor deposition first anode resilient coating; Follow vapor deposition layer of metal layer; Vapor deposition second plate resilient coating is forming anode on this metal level again, and the material of this first anode resilient coating and this second plate resilient coating all is selected from a kind of in organic molecule and the sulfide.
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| CN108461605A (en) * | 2018-06-13 | 2018-08-28 | 浙江西溪玻璃有限公司 | A kind of LED photovoltaic glass substrate |
| CN109524547A (en) * | 2018-10-10 | 2019-03-26 | 华中科技大学 | A kind of preparation method and applications of novel inorganic hole transport layer material |
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