CN101120458B - Solid state photosensitive device using isolated photosynthetic complexes - Google Patents
Solid state photosensitive device using isolated photosynthetic complexes Download PDFInfo
- Publication number
- CN101120458B CN101120458B CN200480044831.3A CN200480044831A CN101120458B CN 101120458 B CN101120458 B CN 101120458B CN 200480044831 A CN200480044831 A CN 200480044831A CN 101120458 B CN101120458 B CN 101120458B
- Authority
- CN
- China
- Prior art keywords
- solid state
- electrode
- state photosensor
- layer
- photosensor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000007787 solid Substances 0.000 title claims abstract description 65
- 108010059332 Photosynthetic Reaction Center Complex Proteins Proteins 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000004065 semiconductor Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 230000005540 biological transmission Effects 0.000 claims description 18
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 6
- 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 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 3
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000005375 photometry Methods 0.000 claims description 2
- 230000005525 hole transport Effects 0.000 abstract 2
- 238000003306 harvesting Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 62
- 150000001875 compounds Chemical class 0.000 description 34
- 238000010672 photosynthesis Methods 0.000 description 26
- 230000029553 photosynthesis Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 108090000623 proteins and genes Proteins 0.000 description 8
- 102000004169 proteins and genes Human genes 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 229930002875 chlorophyll Natural products 0.000 description 7
- 235000019804 chlorophyll Nutrition 0.000 description 7
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical class C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 238000000059 patterning Methods 0.000 description 7
- 239000002800 charge carrier Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 244000061458 Solanum melongena Species 0.000 description 5
- 241001314279 Zoopagales Species 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010023 transfer printing Methods 0.000 description 5
- 108010081996 Photosystem I Protein Complex Proteins 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000005670 electromagnetic radiation Effects 0.000 description 4
- 238000000609 electron-beam lithography Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 210000002377 thylakoid Anatomy 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 241000219315 Spinacia Species 0.000 description 3
- 235000009337 Spinacia oleracea Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000021466 carotenoid Nutrition 0.000 description 3
- 150000001747 carotenoids Chemical class 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000000243 photosynthetic effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 241000192707 Synechococcus Species 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- HRHKULZDDYWVBE-UHFFFAOYSA-N indium;oxozinc;tin Chemical compound [In].[Sn].[Zn]=O HRHKULZDDYWVBE-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000003862 health status Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000005442 molecular electronic Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- -1 polyphenylene ethylene Polymers 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- 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
- H10K85/761—Biomolecules or bio-macromolecules, e.g. proteins, chlorophyl, lipids or enzymes
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- 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
Abstract
Solid state photosensitive devices including photovoltaic devices are provided which comprise a first electrode and a second electrode in superposed relation; and at least one isolated Light Harvesting Complex (LHC) between the electrodes. Preferred photosensitive devices comprise an electron transport layer formed of a first photoconductive organic semiconductor material, adjacent to the LHC, disposed between the first electrode and the LHC; and a hole transport layer formed of a second photoconductive organic semiconductor material, adjacent to the LHC, disposed between the second electrodeand the LHC. Solid state photosensitive devices of the present invention may comprise at least one additional layer of photoconductive organic semiconductor material disposed between the first electrode and the electron transport layer; and at least one additional layer of photoconductive organic semiconductor material, disposed between the second electrode and the hole transport layer. Methods of generating photocurrent are provided which comprise exposing a photovoltaic device of the present invention to light. Electronic devices are provided which comprise a solid state photosensitive device of the present invention.
Description
Technical field
Relate generally to of the present invention comprises the solid state photosensor of photovoltage device, this light-sensitive device comprises into first electrode and second electrode of stacked relation, at least a isolated photosynthesis complexification thing (light capture complexes (LHC), PSI (photosystem I for example, for example from spinach)) and/or the LH2 between these two electrodes (light capture complexes 2 is from the aubergine Zoopagales).Described and comprise exposure photovoltage device of the present invention illumination and provide the method for power, also described including solid state photosensor of the present invention at interior electronic device to circuit.
Background technology
Photosynthesis is the bioprocess that electromagnetic energy is converted to electrochemical energy by light and dark reaction.Photosynthesis betides and is called in green algae and the higher plant in the chlorophyllous special cells device.This chlorophyll is surrounded by two films and contains thylakoid, and the latter is made up of stacked membranous disc (pigment claims) and the membranous disc of lamination (matrix) not.The photosynthesis component that this thylakoid membrane comprises two kinds of keys is photosystem I and photosynthetic body body II, is designated as PSI and PSII respectively.
The forerunner of the electricity research of photosynthesis compound is: Lee and Greenbaum atOak Ridge National Lob.Lee, L, et al, phys, Rev.Lett.79,3294 (1997); Greenbaum, E., science 230,1373 (1985); Lee, L, et al., J.phys.Chem.B 104,2439 (2000).These research workers with chemical method with Pt deposit on the composite surface on the electronics point position, the compound of handling with platinum produces H2 then.They have also measured the orientation statistics of compound on the hydrophily substrate, have observed photovoltage with the Kelvin force microscope simultaneously.Greenbaum，E.，Bioelectrochemistry?andBioenergetics，21：171，1989；Greenbaum，E.，J.Phys.Chem.，94：6151，1990；Lee，L，Proc.Natl.Acad.Sci.USA，92：1965，1995；Lee，I.，et?al.，11(4)：375，1996.See，also，United?Stated?Patent?No.6,162,278，entitledphotobiomolecular?Deposition?of?Met?allic?Particles?and?Films，Hu，December?19，2000.
Molecular circuit be manufactured on the current resolution capability that has exceeded conventional patterning techniques such as electron beam lithography method.But belong to routine with inferior nano-precision in fact to the molecule location, simultaneously then most important for the control of photosynthesis compound.The photosynthesis compound for example focuses on the reaction center that produces electric charge through optimizing with energy from minute sub antenna.The native protein support is being controlled the accurate location and the orientation of the molecule component of optical activity and electronically active.The photosynthesis compound is with size and the degree of functionality by developing and optimizing.For example belong among the Elongtus at typical compound the Synechococcus seen in the aubergine Zoopagales, the photon that is absorbed be with total quantum yield of 98% in the 100ps of photonic absorption IT and.On this whole compound, produced the photovoltage of 1v and power conversion efficiency is about 40%.Schubert，W.D.，et?al，J.Moi.Biol.272，741-768(1997)。In fact, the natural biological molecular complex has surpassed or even the efficient of best artificial light electric device.
But prior art fails to illustrate the efficiency light transformational structure that is used to capture incident light and is converted into the electric energy that is applicable to nano electron device.Still need such solid state photosensor in this technology, thereby they can make photosynthetic protein-based molecule component and comprise that light is converted to photoelectric current provides the conventional electrical device of the photovoltage device of electrical power to be associated to circuit.
Summary of the invention
For this reason, as described herein of the present invention mainly to as if LHC be attached to solid-stately comprise in the function element that adopts single photosynthesis compound (prior art is not susceptible to yet organic layer is attached in the solid state photosensor that includes LHC described herein).
The light-sensitive device that is provided also comprises: by the electron transfer layer 8 that the first photoconductive organic semiconducting materials forms, it is adjacent with LHC6, between first electrode 2 and LCH6; By the hole transmission layer 10 that the second photoconductive organic semiconducting materials forms, it is adjacent with LHC6, between second electrode 4 and LHC6.
Other forms of implementation of the present invention comprise: the photoconductive organic semiconducting materials of another layer at least, and it is between first electrode 2 and electron transfer layer 8; And/or the photoconductive organic semiconducting materials 14 of another layer at least, it is between second electrode 4 and hole transmission layer 10.
The present invention is provided such form of implementation, and electronics wherein and/or exciton barrier-layer 16 are to be located between second electrode 4 and the hole transmission layer 10.
Solid state photosensor of the present invention is preferably: (wavelength X-800nm) is transparent to 2 pairs of incident lights of first electrode wherein basically, organic semiconducting materials between electrode 2 and 4 is transparent to incident light basically, and wherein this second electrode 4 reflects incident light basically.
In the form of implementation of the present invention that provides, the distance that LHC wherein and each electrode are 18 is about λ/4n, and the λ here is the peak wavelength of the light that absorbs of LHC and n is the refractive index of material between LHC and each electrode (2 or 4).
This solid state photosensor also preferably, first electrode 2 wherein also connects second electrode 4 by circuit 20.
The method that produces photoelectric current is provided, and the method comprises photovoltage device exposure of the present invention.
Such electronic device is provided, and they include at least a solid state photosensor of the present invention.
Description of drawings
Fig. 1 illustration solid state photosensor of the present invention.
Fig. 2 generally shows another solid state photosensor of the present invention.
Fig. 3 A generally shows an embodiment of the present invention.
Fig. 3 B is the schematic diagram of several compounds (photovoltage device) of the LHC of interlayer between silver and transparent indium tin oxide.
Fig. 4 shows bright by solid state photosensor one example generation photoelectric current of the present invention.
Fig. 5 shows bright by the routine in addition photoelectric current that produces of solid state photosensor of the present invention.
Fig. 6 shows that bright molecule sensor with the LHC base is generalized to molecular switch.
Fig. 7 shows that bright not damaged die mould technology by ultrahigh resolution directly is transferred to form of implementation on the LHC with metallic contact.
Fig. 8 shows that bright metallic contact being connected by an operation in the not damaged die mould technology of ultrahigh resolution is transferred on the LHC.
Fig. 9 shows that bright metallic contact being connected by another operation in the not damaged die mould technology of ultrahigh resolution is transferred on the LHC.
Embodiment
Unless otherwise prescribed, all here scientific and technical terminology all with general understand identical of the people who is familiar with technology of the present invention.Here the whole publications that provide and the content of patent all are incorporated herein by reference.
Catalogue of the present invention be to provide the efficiency light transformational structure that is used for capturing incident light and is converted into electric energy.The present invention be more particularly directed to such solid state photosensor, it comprises into first electrode and second electrode and at least one the isolated LHC between these two electrodes of stacked relation.Light-sensitive device of the present invention comprises the photovoltage device that light is converted to photoelectric current and thus electrical power is supplied in circuit.The present invention can have various forms of implementation, and they make photosynthetic protein-based molecular components be associated with traditional electronic device.The present invention is specially adapted to nano level light-sensitive device, comprises transducer, photocell and relevant therewith device.Main purpose of the present invention is LHC is combined in the function element that comprises the device that adopts single photosynthesis compound.The nanoscale photo-detector and the photocell that are used for nano-device are provided.
Referring to Fig. 1, solid state photosensor of the present invention specifically includes into first electrode 2 and second electrode 4 and at least one isolated LHC6 between these two electrodes of stacked relationship.Form of implementation of the present invention for example also can comprise: by the electron transfer layer 8 that the first photoconductive organic semiconducting materials forms, it is adjacent with LHC6, between first electrode 2 and LHC6; By the hole transmission layer 10 that the second photoconductive organic semiconducting materials forms, it is adjacent with LHC6, between second electrode 4 and LHC6.Other forms of implementation of the present invention comprise: the photoconductive organic semiconducting materials 12 of another layer at least, and it is between first electrode 2 and electron transfer layer 8; And/or the photoconductive organic semiconducting materials 14 of another layer at least, it is between second electrode 4 and hole transmission layer 10.
Referring to Fig. 2, the present invention is provided such form of implementation, exciton barrier-layer 16 wherein is to be located between second electrode 4 and the hole transmission layer 10.Solid state photosensor of the present invention is preferably: (the substantial transparent of wavelength X-800nm) of 1 pair of incident light of first electrode wherein, photoconductive organic semiconducting materials between electrode is to the incident light substantial transparent, and wherein this second electrode 4 reflects incident light basically.In the form of implementation of the present invention that provides, LHC wherein and each distance between electrodes 18 are about λ/4n, and the λ here is the peak wavelength of the light that absorbs of LHC and n is the refractive index of material between LHC and each electrode.Solid state photosensor then preferably makes first electrode 2 wherein also link to each other with second electrode 4 by circuit 20.
Particularly utilized the progressive optimizing process of photosynthesis compound that effective power transfer is provided.LHC is positioned in the solid state photosensor of the present invention photosynthesis reagent with inferior nano-precision, and makes up for this device provides the biomolecule electronics.Pinpoint molecule interacts by dipole-dipole coupling (being similar to antenna and receiver) in LHC component of the present invention.This coupling is responsive especially to molecule position and orientation.The extra small size has here reduced switching energy and transit time.Noun " light capture complexes " (LHC) is meant such photosynthesis compound such as PSI (photosystem I is for example from spinach) at this, and/or LH2 (light capture complexes 2, from the purple Zoopagales), Fromme, P., et al.Biochim.Biophys.Acta 1365,175 (1998); Lee, L, et al, phys.Rev.Lett.79,3294 (1997); Schubert, W.D.et al, J, MoI Biol.272,741-768 (1997).This class compound can be from buying on the market, for example can be available from PROTEINCABS Inc., and 1425Russ Blvd., Suit T-107C, San Diego, CA92101.Photosystem I (PSI) is for example preferably got LHC in the structure of the solid state photosensor of the present invention that comprises logical device.Example as used in the present invention PSI preferably from for example spinach chlorophyll.PSI is a kind of protein-chlorophyll compound of the diodic of having character, is the part of photosynthesis mechanism in the thylakoid membrane.Its ovalize, size are about 5 * 6 nanometers.PSI is used for setting up the nanometer circuit at this.This PSI reaction center/fuse antenna compound contains about 40 chlorophyll of every photosensitized reaction center pigment (P700).Chlorophyll molecule is as absorbing photon and luminous energy being transferred to the antenna of P700, and this luminous energy is hunted down and is used to drive photochemical reaction.Except that P700 and antenna chlorophyll, this PSI compound comprises many electronics to be led.The electronics that disengages from P700 moves to terminal acceptor by the reducing end of middle acceptor in PSI, and this electron transport is passed through thylakoid membrane then.Electron transfer is to the stromal surface of PSI and the hole is retained in the light-emitting area of PSI.After absorbing photon, this energy is just guided the primary electron donor to this compound pedestal.After the exciton disassociation, electronics is by three Fe
4S
4Bunch move on the facing surfaces.There is electronics in the result and has the hole on surface, bottom (luminous) on surface, top (matrix).Therefore, because the directive property of electron transfer, this kind compound is preferably in to be deposited to has correct orientation when go up on the surface.Lee, the work measurement of et al. PSI compound selectively deposited on hydrophilic surface be with the electron transfer vector perpendicular to agent-phys.Rev.Lett.79,3294-3297 (1997).
For the PSI reaction center, the mid point oxidation potential energy that is produced by primary electron donor (P700) is about+0.4v and be that the corresponding reduction potential that electronics is produced by main (4Fe-4S center) is about-0.7v.So this PSI reaction center is the solar cell of a photodiode (unidirectional electron stream) and nanoscale (about 6nm).
Another kind of important compound is to be used for the LHC of absorbed radiation solar energy for aubergine Zoopagales (being belonged to acidophil by the aubergine single-cell bacteria).This LHC has separated out and crystallization Cogdel, R.J., et al., Biochimica et Biophysica Acta 722,427-435 (1984); McDermott, G., et al., Nature 374,517-521 (1995); Papiz, M.Z., et al, Journal of Molecular Biology 209,833-835 (1989); Fenna, R.E., et.al., Nature 258,573-577 (1975).The photosynthesis mechanism of above-mentioned bacterium is through biological method optimization, makes energy focus on reaction center in 100ps and total amount and productive rate is 98%.Sundstrom，V.，et?al.，Journal?of?Physical?Chemistry?B103，2327-2346(1999)；Renger，T.，et?al.，Physics?Beports?343，137-254(2001)。This protein has multiple use.It gives the photosynthesis unit with rigidity, chromatopexis should be had the position, is that surplus heat provides radiator in it.The photosynthesis unit proceeds to gradually can revolt degeneration, and the pigment that for example is referred to as carotenoid can significantly improve the stability of photosynthesis unit by quenching triplet (preventing from might form singlet oxygen by triplet-triplet disappearance).As described above these can be used as photo-detector and photronic component described here in the photosynthesis compound.
Come from aubergine Zoopagales Synechococcus and belong to that known biomolecule compound photosynthetical system I (PSI) is another example that is used for the LHC of solid state photosensor of the present invention among the Elongtus.Schubert，W.D.et?al.，J.MoI?Biol.272，741-768(1997)。PSI preferentially forms the tripolymer compound.At the center of each PSI monomer, produce electric charge at the reaction center place.Around this reaction center 100 chlorophyll molecules are arranged approximately.These molecule absorption light also direct into this center with it, play the effect of efficient antenna.Also have 15-25 carotenoid molecule, they have absorbing light under the wavelength of muting sensitivity at chlorophyll molecule, and these carotenoid go out suddenly by the formation that makes singlet oxygen and avoid the structure oxidation.PSI can individualism or can be combined with other LHC and exist, and has so just strengthened its absorbability under low luminosity class.
Because the LHC reaction center is pigment-protein complex, this class reaction center such as the described here component that be used as all different components of decision luminous energy to the photosynthesis conversion of electric energy.
The invention provides a kind of like this solid state photosensor, it comprises that at least one connects first electrode and the isolated LHC that is connected second electrode with electronics method independently with electronics method.Such photovoltage device also is provided, and it comprises that at least one connects first electrode and the isolated LHC that is connected second electrode with electronics method independently with electronics method, and wherein this first electrode also is connected with second electrode by circuit.Solid state photosensor of the present invention comprises into first electrode and second electrode and at least one isolated LHC between these two electrodes of stacked relation.The invention provides a kind of system, it is caught light with the separation of charge method and is used for photosynthesizer, but also is used as effective light-current converter in molecular device.
The electrode or the contact that are used for solid state photosensor of the present invention are the special attention of needs.Preferably can allow the environment electromagnetics radiation of maximum be sent to photoconductive active internal district from this device outside.In other words, preferably can make electromagnetic radiation arrive it and can absorb the place that is converted to electricity by photoconduction.This shows the minimum absorption of electromagnetic radiation and the minimum reflection of at least one reply incident of these electric contacts usually.It is transparent to that is to say that this contact should come down to." electrode " and " contact " speech of etc.ing only are meant some layers like this with here the time, and they provide intermediary's means or provide bias voltage to this device to external circuit for conveying light generation power.That is electrode or contact be between the photoconductive active region and lead, lead-in wire, trace or other devices of solid state photosensor, provides to be used for carrying or the interface of output charge carrier with respect to external circuit." charge transfer layer " speech is meant with electrode that at this certain similar layer is arranged, but different be that from then on charge transfer layer only is transported to adjacent subarea in a subarea of device with charge carrier.A series of so-called here organic material layer or some different material layers is " transparent ", refers to when this class layer can allow environment electromagnetics radiation under at least 50% relevant wavelength and has through this class layer.Similarly, when can seeing through the environment electromagnetics radiation be less than under 50% the relevant wavelength, this class layer claims that then this class layer is " translucent ".
That electrode or contact are generally metal or " metallic alternatives ".The speech here " metal " is used for comprising the simple metal Mg and by the metal alloy compositions formed of Mg and Ag and be designated as Mg:Ag for example of the simple metal under two or more element meanings together for example under the element meaning.The speech here " metallic alternatives " refers to the material of metal under a kind of non-common definition, but this material has the character of required metalloid in some suitable application.The metallic alternatives that generally is used for electrode and charge transfer layer will comprise the semiconductor of the broad-band gap of doping, for example transparent conductive oxide such as tin indium oxide (ITO), oxidation gallium indium tin (GITO) and zinc indium tin oxide.Particularly ITO is highly doped degeneracy n
+Semiconductor has the optical band gap of about 3.2ev, makes it to see through the wavelength greater than about 3900 dusts.The another kind of metal substitute material that is suitable for is transparent conducting polymer polyaniline (PANI) and chemical correlative thereof.Metallic alternatives can also be chosen from the nonmetallic materials of wide scope, and wherein " nonmetal " speech is used for comprising that a vast class is not the material of no metal under the chemical combination form at it.When a kind of metal is present under its uncombined form or separately or be combined with one or more other metals and during as a kind of alloy, this metal or also can think that it is to be under its metallic forms or " free metal ".Like this, metallic alternatives electrode of the present invention can be called " no metal " sometimes, and " no metal " speech then is included in its not material of no metal under the chemical combination form.Free metal has such metallic bond form usually, and this metallic bond can be thought such class chemical bond, and they are from a large amount of valence electrons that can move freely along the different band of electronics in whole metal lattice.Though metallic alternatives can contain metal component, they are " nonmetal " based on several reasons.They are not pure free metals, alloy that neither free metal.When metal occurred with their metallic forms, the electronics conduction band also provided high conductivity together with other metallines and to the high reflectivity of light radiation.
Described first electrode is preferably to the incident light (substantially transparent of wavelength X-800nm) for example.This first electrode can comprise the ITO that tin indium oxide (ITO) for example or degeneracy mix.Other suitable material includes but not limited to for example ZnO, TiO
2, Ag, Au and Pt.
Described second electrode is preferably to incident light (for example wavelength X-800nm) fundamental reflection.This reflective electrode can comprise for example film of subordinate's metal: Al, Ag or Au, In, Mg, Mg: Ag (1: 10), the 0.5nm LiF/100nm Al of Ca or lamination.
Here used speech organic layer or layer are meant photoconduction electricity organic semiconducting materials." semiconductor " speech herein is meant the material that conductivity can be arranged when inducting charge carrier owing to heat or electromagnetic excitation.Aforementioned " photoconduction " speech relates generally to following process: electromagnetic radiation energy is absorbed and is converted to the excitation energy of charge carrier, makes this charge carrier to conduct in material and promptly moves electric charge." photoconductor " is to be used to refer to such semi-conducting material with " photoconductive material " at this, and they have the electromagnetic radiation of the frequency spectrum energy that can absorb selection to produce the character of charge carrier.
Light-sensitive device of the present invention also can comprise: by first electron transfer layer that form of photoconduction organic (layer) semi-conducting material, it is adjacent with LHC, between first electrode and LHC, and/or the hole transmission layer that forms by the second photoconductive organic semiconducting materials, it is adjacent with LHC, between second electrode and LHC.
Electron transfer layer can be by photoconductive organic semiconductor 3,4,9,10 times of tetracarboxylic bisbenzimidazoles (PTCBI) for example.Other are applicable to this purpose generally can extract electronics and/or include but not limited to for example BCP, AIq for the material that electronics has a high affinity
3, CBP, Fi
6CuPc, C
60, PTCBI and PTCDA.
Hole transmission layer can by second photoconduction electricity organic semiconductor for example copper phthalocyanine (CuPc) form.Other materials that are applicable to that this purpose generally can be applied to electronics and/or have a low ionization potential include but not limited to for example α NPD.TPD, CuPc, CoPc and ZnPc.
In solid state photosensor of the present invention, between first electrode and electron transfer layer, be provided with the photoconduction electricity organic semiconducting materials of one layer or more (can reach 5 layers) in addition.Similarly, between second electrode and hole transmission layer, can be provided with the photoconductive organic semiconducting materials of one layer or more (can reach 5 layers) in addition.The function of these layers includes but not limited to separate layer (being used to optimize optical interference), barrier layer and dynode layer.
The form of implementation of above-mentioned solid state photosensor preferably makes the distance of LHC and each electrode be about λ/4n, and wherein n is the refractive index (n generally makes an appointment with～1.7) of material between LHC and each electrode.
Other forms of implementation of solid state photosensor of the present invention are located between second electrode and the LHC with the adjacent hole transmission layer of LHC except that having, and also comprise the exciton barrier-layer of the photoconductive organic semiconducting materials between second electrode and cave, cave migrating layer.The exciton barrier-layer examples of material includes but not limited to 2,9-dimethyl-4,7-hexichol-1,10-phenanthroline (BCP); 4,4 ', 4 " three { N ,-(3-aminomethyl phenyl)-N-phenylamino } triphenylamines (m-MTDATA); And polyethylene dioxythiophene (PEDOT).Referring to, Forrest, et al., U.S. Patent No. 6 451415 is inscribeed one's name and is " organic photosensitive optoelectronic devices with exciton barrier-layer ".
Other forms of implementation of above-mentioned solid state photosensor are envisioned for: wherein first electrode has and can allow light enter the hole of LHC.Solid state photosensor of the present invention can utilize concentrator that light is introduced LHC.The structure that is designed to be used for light is trapped in it can generally be referred to as waveguiding structure, or also is referred to as optics cavity or reflection cavity.The light thing that can circulate repeatedly in this optics cavity or waveguiding structure is particularly conducive to the structure of using the organic photosensitive material, and this is can not sacrifice conversion efficiency because adopting photoactive layers as thin as a wafer.The light that imports is hunted down and circulation repeatedly, makes the light absorption maximization by the light-sensitive material that comprises it.The purpose of this feature is to increase the light that is gathered, and is provided for the efficiency light transformational structure of catching incident light and being converted into electric energy simultaneously, and another purpose is to provide the efficiency light transformational structure of the parabolic condenser that utilizes general conical.Another purpose provides utilizes the roughly efficiency light transformational structure of the parabolic condenser of flute profile.Another purpose provides the efficiency light transformational structure with a series of concentrators and waveguiding structure, and with the surfaces externally and internally of this concentrator is used for concentrating and then circulation is caught light radiation.Referring to Forrest et al, U.S. Patent No. 6333458, inscribeing one's name is " high-efficiency multiple with concentrator reflects photosensitive optoelectronic devices ".
Here used circuit one speech has its ordinary meaning, thereby refers to any circuit that comprises capacitor and comprise load or the circuit of outer load.Sort circuit can apply external voltage.Photovoltage device of the present invention has such character: when they are connected with load and are rayed, just produce photovoltage and/or photoelectric current.Fig. 4 and 5 illustrations produce photoelectric current by solid state photosensor example of the present invention.
Solid state photosensor of the present invention is converted to light.Above-mentioned device of the present invention for example comprises optics, switch, transducer, gate and the energy.Provide solid-state light voltage (PV) device to produce electrical power especially.These devices are used for driving the load of consumed power.Utilize the solid state photosensor of the present invention can drive electronics such as computer or remote control or communication equipment.Many application examples of nanoscale circuit are as needing distributed power supply and photo-detector.The small size of aforementioned molecular complex can be served the purposes based on this class material ideally, aspects such as design and functional exploitation, the application of this generating direction may also relate to energy accumulating device, can not when the sun or other environment light sources obtain direct lighting operation being continued.The solid state photosensor that is equiped with light-sensitive device of the present invention includes but not limited to the molecular circuit system of optical drive; Solar cell, photometry is calculated and gate; Optoelectronic switch; Survey for example the electronic light sensors sensitization and the photon A/D converter of light, chemicals, toxin, pathogen and healing potion.Light-sensitive device of the present invention can be used as for example local energy of treatment element of nano-scale systems.Photocell of the present invention for example may diminish to diameter 10ran.
Light-sensitive device of the present invention can be assembled in the sensor device, is used for surveying health status, pathogen and/or organism such as bacterium and virus.The photosynthesis compound can match with the biological and chemical system, and the photovoltage energy can be for Application in Sensing.Transducer for example can be adopted as biology or the chemical method of surveying biological or chemical reagent delicately and developing or design, and its response for example can be that the variation of electric current, voltage, electric capacity, inductance, light output maybe can be the variation that absorbs.The existence of analyte (intending the material of detection) will be switched on or switched off photoresponse or change and absorb or the change emission spectrum.The link naturally between these transducers and the structure of compound such as photosynthesis compound just are utilized according to aforesaid way.
Fig. 6 shows and bright LHC base molecule sensor is expanded to molecular switch, wherein relates to the structure of LHC base molecule sensor and logic element.In these two kinds of situations all is to provide energy with optical means.This structure has constituted the basis of no lead computer, and signal wherein is by the carrying of molecule circuits for triggering.For carrying out logical operation, the output of a LHC unit should be the input of another LHC.This can be used to produce the molecule circuits for triggering with regard to this photosynthesis of demand unit or this LHC is necessary for signal of telecommunication quencher.LHC is used to generate the molecule circuits for triggering that lead to next photosynthesis unit from a photosynthesis unit, constitutes the basis that " no lead " calculates.
Example
Care should be used to does not disturb the protein scaffolds of LHC when being set to metallic contact on the LHC.For this purpose, for example adopted nondestructive nano metal contact die mould technology.The protein-based compound of this kind is by the conventional electronic component that adopts the nano-patterning technology.For example referring to Kim, et al, U.S.Patent No.6,468,8 19, Method For Patterning OrganicThin Film Devices Using A Die; And, Lee, et al., ProgrammableNanometer-Scdale Electrolytic Met al Deposition And Depletion, U.S.Patent No.6,447,663, wherein the content of each document is incorporated herein by reference.
Example 1
This device is to constitute (" growing into ") from a side.For example electrode can at first be deposited on the substrate (for example glass or plastics).The PSI compound for example can be deposited on the transparent indium-tin oxide electrode.Metallic contact to a LHC PSI compound for example can be by the direct transfer printing of not damaged die mould technology of ultrahigh resolution.The metallic contact that forms must be complementary with fragility protein (LHC) compound.The purpose of above-mentioned technology is the contact point place between lithographic patterning die mould and substrate, with resolution (about 10nm) the transfer printing metal film that is equivalent to PSI compound diameter.Make transfer printing can take place as long as the bonding force of substrate-metal surpasses the bonding force of die mould and metal level.In order to improve transfer printing, the bonding layer that weakens of one layer or more can be set between die mould face and metal level as teflon, referring to Fig. 7 (Fig. 7-9).Before step 1, with vacuum evaporation or sputtering method deposit thin layer (＜50) metal.This " butt " layer is thinned to the damage that is enough to make to any fine-feature of substrate and reduces to minimum.In step 1, make the die mould butt layer contact therewith of metal coating, at these contact point place transfer printing metals.By bonding weakening can be improved transfer efficiency and can economize and remove the butt layer between layer insertion die mould and the metal coating thereof.After step 2 is removed die mould, remove the material that touches of any exposure simultaneously with the Ar sputter in the substrate of step 3 etching patterning.Referring to: U.S.Patent No.6,468,819, Method ForPatterning Organic Thin Film Devices Using A Die; And, Lee, et ai, Programmable Nanometer-Scdale Electrolytic Met al Deposition AndDepletion, U.S.Patent No.6,477,663.Though be basically in this example with the metal deposition of electrode as first step (electrode), also can the metal deposition of electrode as the final step in this building method." electrode " speech here is the generic term of " first electrode " or " second electrode ", also is like this in the appended claim book.
Example II
Above-mentioned electrode for example can pass through the photoetching technique patterning.But patterning can be finished in the electrodeposition step among the routine I simultaneously.Fig. 3 has generally shown the compound (photovoltage device) of several LHCs of interlayer between silver and transparent indium tin oxide (TIO) film.This TIO can be by exposing from the LHC individual layer of combination and by the electron beam lithography patterning, making the bond property that has changed LHC like this.The contact size of die mould form is determined by the electron beam lithography method.The shape of being determined protuberance by the electron beam lithography method on die mould is that the one skilled in the art is known, wherein relate to resist (polymer is generally the PMMA-polymethyl methacrylate) be exposed to thin (～1nm) under the electron beam.Exposure place of resist will be dissolved under Weak solvent and be allowed unexposed part keep intact.By wet method or dry etch technique the resist pattern is redirect on the die mould then.
Example III
Above described electrode, for example can add for example 1-5 layer organic layer by hot evaporation.LHC can interlayer between charge migration film organic material.Because LHC needs solution-treated, the supporting organic layer preferably hydrophobic charge transfer polymerization thing adjacent (for example PPV (polyphenylene ethylene base) or PEDOT:PSS (polyethylene dioxythiophene: polystyrene-sulphonic acid ester)) with LHC.The top layer adjacent with LHC can be made by a spot of molecular material of vacuum evaporation, conflicts with the polymer and the LHC of lower floor to avoid solvent.Above-mentioned organic layer is preferably transparent to incident light.Therefore, this heterostructure can be ignored when not having LHC the photovoltage effect of visible light.Each active optical molecule for example contacts with organic film.For example can grow one to multiple layer (for example five layers) molecular layer with vacuum technique.S.R.Forrest，Chem.Rev.vol.97，p?1793(1997)。
Example IV
At least a LHC of deposit for example PSI or LH2 on the organic layer of going up most.
The electro-deposition system that is used for adjusting deposit (for example LHC) preferably includes into two electrodes of stacked relation.Under the electro-deposition condition, have low pole or do not have maybe can the induct material of polarity of polarity, can covalently link suitable charged carriers to form the charged compound that can be deposited on the electrode.The solution of deposit or suspension can be the aqueous solution such as physiological saline, can conduct significant electric current.The direction of the deposit during beginning in deposit solution or suspension, mobility and deposition rate, can passing through suitably, the pH of regulator solution controls with very big sensitivity.The pH of this solution or suspension is adjusted to the isoelectric point that is higher or lower than the deposit of intending deposit.This adjusting can be finished with known acidity or alkaline reagent as required.Also can in this solution, add other additives such as nonionic surfactant and anti-blowing agent or washing agent as required.Electrode can be formed or " metallic alternatives " is attached on the substrate and forms by metal.Substrate can be organic or inorganic, biological or combination in any abiotic or this class material.The material that is applicable to substrate comprises silicon, silicon dioxide, quartz, glass, controlled porous glass, carbon, aluminium oxide, carbon dioxide, germanium, silicon nitride, zeolite and GaAs." metal " speech is used for comprising simple metal for example Ag or Mg and by the metal alloy compositions formed of Mg and Ag and be designated as Mg:Ag for example of the simple metal under two or more element meanings together under the element meaning at this.The speech here " metallic alternatives " refers to the material of metal under a kind of non-common definition, but this material all has required metal-like properties in some suitable application.The suitable metallic alternatives that can be used for electrode comprises the semiconductor of the broad-band gap of doping, for example transparent conductive oxide such as tin indium oxide (ITO), oxidation gallium indium tin (GITO) and zinc indium tin oxide (ZITO).Other are applicable to that the material of electrode is aggretion type metal such as the polyethylene dioxythiophene (PEDOT) that mixes with polystyrolsulfon acid ester (PSS).It is constant electric current to provide between two electrodes basically that power supply with the negative lead-in wire that just goes between and be connected with another electrode that is connected with one of electrode is provided, and two interelectrode distance D i can be about 10nm～about 5.0mm.As long as the surplus region insulation of substrate just can be carried out deposit on nano level electrode.Suitable distance D i is about 1.0mm.The voltage that is applied on the electrode depends on this distance D i.For example the voltage that can apply is that about 1v/cm is to about 1000v/cm.When being about 1mm for interelectrode distance D i, suitable voltage is the about 200v/cm of about 10v/cm-.Between two electrodes, be provided with the solution or the suspension of deposit.This voltage is to apply a scheduled time continuously so that the deposit entity can be shifted to an electrode deposited film of deposit is provided.For example, can apply voltage continuously about 5 minutes to about 48 hours.Added voltage depends on the thickness of required deposit and is used for the concentration of solution of electro-deposition deposit, has found that, is preferably in and adopts minimum distance to reduce required voltage between two electrodes.Select the concentration of deposit in its solution or suspension and the volume of this solution, in order to be controlled at the thickness that applies this deposit under the predetermined voltage continuously.Can select the concentration of deposit in solution or suspension on one of electrode, to form monofilm.Deposit that can deposit 100% on an electrode in a kind of form of implementation of the present invention, this moment, the concentration of used deposit was about 10 μ g/ml～about 1mg/ml, the about 1mm of volume
3～about 100mm
3And the about 10v/cm of voltage～about 200v/cm, the about 5nm of formed individual layer thickness～about 10nm.Should know by change deposit in solution or suspension concentration and the volume of this solution be deposit to become thicker film.Can be with solution or the suspension of maintenance case so that the deposit predetermined to be provided of a selected size.For example can make this keep case that about 1mm is provided
3～about 100mm
3Volume.The migration of deposit occurs in deposit charging side to the electrode that charges and goes up in the opposite direction.Deposit is because it and interelectrode van der Waals interaction and can be attached on the electrode in large quantities.Fixed deposit can be used for any related device, and the fixed deposit here then is that this device of running is requisite.Suitable device comprises solid state device, memory device and photovoltage device.
Can deposit individual layer LHC, for example adopt the common spin coating technique in the aqueous solution.
The functional orientation of LHC is very important, and this is because the light stimulus meeting produces electronics and produces the hole on (chamber) surface down in it on (matrix) surface on the LHC.Must be orientated suitably when therefore, LHC is on being deposited on substrate (this should according to concrete purposes).This can realize by the electrostatic precipitation technology, because above-mentioned both sides up and down can have different charge density charge polarity not even together.Other possibility is for the affinity of the special base on the protein or covalent bonding (these bases can be that the compound dna technique that maybe can pass through that nature exists inserts).For example, U.S. Patent No. 6231983 " orientation methods of molecular electronic components and parts " (Lee et al., May 15 calendar year 2001) is the method at PSI reaction center orientation on substrate.This method comprises the surface modification that makes substrate and is able to the PSI reaction center is fixed by selected direction.Add the solution that comprises the PSI reaction center then, and this PSI is just according to selected direction orientation.This selected direction can be parallel to substrate surface, in " making progress " position perpendicular to this surface or in " down " position perpendicular to this surface.The decision of selected direction should be according to the required purposes of substrate.
Example V
Can for example organic layer be added on the upper surface of LHC of deposit by the hot evaporation described in the routine III.
Example VI
Can set up top electrodes with the nanometer die mould technology among the routine I for example.
More than all publications and its content of patent of addressing in the explanation all is incorporated herein by reference.All corrections of composition of the invention described above and method and modification do not depart from the scope of the present invention with spirit under be that the one skilled in the art understands.Although the present invention is described in conjunction with concrete best form of implementation.But will be appreciated that the present invention is not subjected to the limit of these concrete forms of implementation.In fact, for implementing composition and the mode that the present invention illustrates, their all remodeling is that one skilled in the art institute clearly so all should belong within the scope of appended claim book in this technology or the association area.
Claims (28)
1. solid state photosensor, it comprises:
Become first electrode and second electrode of stacked relation;
The light capture complexes that between these two electrodes at least one is isolated;
By the electron transfer layer that the first photoconductive organic semiconducting materials forms, it is adjacent with the light capture complexes, between this first electrode and light capture complexes; And
By the hole transmission layer that the second photoconductive organic semiconducting materials forms, it is adjacent with the light capture complexes, between this second electrode and light capture complexes.
2. according to the solid state photosensor of claim 1, it also comprises: the photoconductive organic semiconducting materials of another layer at least between this first electrode and electron transfer layer.
3. according to the solid state photosensor of claim 1, it also comprises: the photoconductive organic semiconducting materials of another layer at least between this second electrode and hole transmission layer.
4. according to the solid state photosensor of claim 2, it also comprises: the photoconductive organic semiconducting materials of another layer at least between this second electrode and hole transmission layer.
5. according to the solid state photosensor of claim 3, wherein the photoconductive organic semiconducting materials layer between this second electrode and hole transmission layer is an exciton barrier-layer.
6. according to the solid state photosensor of claim 1, wherein this first electrode has the hole that photoconduction can be guided to the light capture complexes.
7. according to the solid state photosensor of claim 2, wherein this at least the photoconductive organic semiconducting materials of another layer have the hole that photoconduction can be guided to the light capture complexes.
8. according to the solid state photosensor of claim 6 or 7, it also comprises and is used for photoconduction is drawn concentrator to the light capture complexes.
9. according to the solid state photosensor of claim 1, wherein to be about the incident light of 800nm be transmission to the first electrode pair wavelength substantially.
10. according to the solid state photosensor of claim 1, the incident light that the second electrode pair wavelength wherein is about 800nm reflects substantially.
11., be transmission substantially to the incident light that wavelength is about 800nm wherein at two interelectrode photoconductive organic semiconducting materials according to the solid state photosensor of claim 4.
12. according to the solid state photosensor of claim 9, wherein this first electrode comprises the doped ITO of degeneracy.
13. according to the solid state photosensor of claim 10, wherein this second electrode comprises metal film, this metal film comprises Al, Ag or Au.
14. according to the solid state photosensor of claim 1, wherein this electron transfer layer comprises and is selected from PTCBI, BCP, AIq
3, CBP, F
16CuPc, C
60With the material in this group of PTCDA.
15. according to the solid state photosensor of claim 1, wherein this hole transmission layer comprises the material that is selected from this group of α NPD, TPD, CuPc, CoPc and ZnPc.
16. according to the solid state photosensor of claim 2, wherein this one deck at least photoconduction organic semiconducting materials layer between first electrode and electron transfer layer comprises and is selected from PTCBI, BCP, AIq
3, CBP, F
16CuPc, C
60With the material in this group of PTCDA.
17. according to the solid state photosensor of claim 3, wherein this photoconduction of one deck at least organic semiconducting materials layer between second electrode and hole transmission layer comprises the material that is selected from this group of α NPD, TPD, CuPc, CoPc and ZnPc.
18. according to the solid state photosensor of claim 5, wherein this exciton barrier-layer comprises and is selected from 2,9-dimethyl-4,7-hexichol-1,10-phenanthroline; 4,4 ', 4 " three { N ,-(3-aminomethyl phenyl)-N-phenylamino } triphenylamines; And the material in the group of polyethylene dioxythiophene.
19. according to the solid state photosensor of claim 1, wherein this light capture complexes is selected from PSI and this group of LH2.
20. according to claim 1 or 4 described solid state photosensors, wherein be about λ/4n in light capture complexes and each interelectrode distance, and this λ is a kind of important optical wavelength that the light capture complexes is absorbed, and n is the refractive index of light capture complexes and each interelectrode material.
21. according to the solid state photosensor of claim 1, wherein this first electrode also is connected to this second electrode by circuit.
22. according to the solid state photosensor of claim 21, wherein this solid state photosensor is a photovoltage device.
23. according to the solid state photosensor of claim 1, it also comprises the light capture complexes of individual layer.
24. according to the solid state photosensor of claim 1, it also comprises single light capture complexes.
25. a method that produces photoelectric current, the method comprise the photovoltage device exposure with claim 22.
26. a method of giving circuit supply, the method comprise the photovoltage device exposure with claim 22.
27. an electronic device, it comprises the solid state photosensor of claim 21.
28. according to the electronic device that comprises solid state photosensor of claim 27, wherein, described electronic device is selected from this group of solar cell, photometry calculation and gate, optoelectronic switch, electronic type optical sensor and photon A/D converter.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2004/040327 WO2006060017A1 (en) | 2004-12-02 | 2004-12-02 | Solid state photosensitive devices which employ isolated photosynthetic complexes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101120458A CN101120458A (en) | 2008-02-06 |
| CN101120458B true CN101120458B (en) | 2010-10-06 |
Family
ID=34959651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480044831.3A Expired - Fee Related CN101120458B (en) | 2004-12-02 | 2004-12-02 | Solid state photosensitive device using isolated photosynthetic complexes |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1817800A1 (en) |
| JP (1) | JP2008522428A (en) |
| CN (1) | CN101120458B (en) |
| AU (1) | AU2004325239A1 (en) |
| CA (1) | CA2589347A1 (en) |
| MX (1) | MX2007006651A (en) |
| WO (1) | WO2006060017A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006090381A1 (en) | 2005-02-22 | 2006-08-31 | Ramot At Tel Aviv University Ltd. | Molecular optoelectronic device and method of fabricating the same |
| US8624227B2 (en) | 2005-02-22 | 2014-01-07 | Ramot At Tel-Aviv University Ltd. | Optoelectronic device and method of fabricating the same |
| GB2439774A (en) * | 2006-04-19 | 2008-01-09 | Graham Vincent Harrod | Solar cell using photosynthesis |
| US8987589B2 (en) * | 2006-07-14 | 2015-03-24 | The Regents Of The University Of Michigan | Architectures and criteria for the design of high efficiency organic photovoltaic cells |
| WO2008023372A2 (en) * | 2006-08-22 | 2008-02-28 | Ramot At Tel Aviv University Ltd. | Optoelectronic device and method of fabricating the same |
| DE102007009995A1 (en) * | 2007-03-01 | 2008-09-04 | Hahn-Meitner-Institut Berlin Gmbh | Organic solar cell comprises two electrodes and disposed between photoactive layer having two partial layers, where partial layer emits electrons and later partial layer receives electrons |
| WO2008114249A1 (en) * | 2007-03-16 | 2008-09-25 | T.O.U Millennium Electric Ltd. | Solar power generation using photosynthesis |
| CN101802948B (en) * | 2007-07-23 | 2014-01-15 | 巴斯夫欧洲公司 | Photovoltaic tandem cell |
| WO2010137013A1 (en) * | 2009-05-27 | 2010-12-02 | Ramot At Tel Aviv University Ltd. | Crystallized photosystem i units from the pea plant and their use in solid state devices |
| US8962994B2 (en) * | 2010-10-22 | 2015-02-24 | Xerox Corporation | Photovoltaic device |
| US8952372B2 (en) * | 2011-12-28 | 2015-02-10 | Panasonic Corporation | Photoelectric element and method for producing the same |
| JP6115953B2 (en) * | 2013-07-02 | 2017-04-19 | 国立研究開発法人産業技術総合研究所 | Method for producing a structure having a large number of nano metal bodies transferred on the surface |
| FR3085792B1 (en) * | 2018-09-07 | 2021-11-05 | Commissariat Energie Atomique | MULTI-LAYER STRUCTURE ESPECIALLY FOR PHOTOVOLTAIC CELLS, INTEGRATING A SELF-ASSEMBLED MOLECULAR SINGLE-LAYER, SAM |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6333458B1 (en) * | 1999-11-26 | 2001-12-25 | The Trustees Of Princeton University | Highly efficient multiple reflection photosensitive optoelectronic device with optical concentrator |
| US6451415B1 (en) * | 1998-08-19 | 2002-09-17 | The Trustees Of Princeton University | Organic photosensitive optoelectronic device with an exciton blocking layer |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4360703A (en) * | 1981-04-28 | 1982-11-23 | National Research Council Of Canada | Photovoltaic cell having P-N junction of organic materials |
| JPS629228A (en) * | 1985-07-05 | 1987-01-17 | Matsushita Electric Ind Co Ltd | Photoelectric conversion device |
| JPH0612815B2 (en) * | 1989-04-24 | 1994-02-16 | 工業技術院長 | Method for producing photoelectric conversion element using functional protein complex |
| JPH03205520A (en) * | 1989-10-18 | 1991-09-09 | Fuji Photo Film Co Ltd | Photoelectric converting element |
| JPH0797044B2 (en) * | 1991-05-16 | 1995-10-18 | 工業技術院長 | Photoelectric conversion element and method for manufacturing the same |
| JP2677298B2 (en) * | 1992-06-30 | 1997-11-17 | スタンレー電気株式会社 | Photoelectric conversion device using biopolymer composite |
| US6580027B2 (en) * | 2001-06-11 | 2003-06-17 | Trustees Of Princeton University | Solar cells using fullerenes |
| GB0222510D0 (en) * | 2002-09-27 | 2002-11-06 | Riso Nat Lab | Conducting polymer devices for inter-converting light and electricity |
| CN1774823B (en) * | 2003-03-19 | 2010-09-08 | 赫里亚泰克有限责任公司 | Photoactive component comprising organic layers |
-
2004
- 2004-12-02 AU AU2004325239A patent/AU2004325239A1/en not_active Abandoned
- 2004-12-02 WO PCT/US2004/040327 patent/WO2006060017A1/en active Application Filing
- 2004-12-02 EP EP04812770A patent/EP1817800A1/en not_active Withdrawn
- 2004-12-02 JP JP2007544319A patent/JP2008522428A/en active Pending
- 2004-12-02 MX MX2007006651A patent/MX2007006651A/en unknown
- 2004-12-02 CN CN200480044831.3A patent/CN101120458B/en not_active Expired - Fee Related
- 2004-12-02 CA CA002589347A patent/CA2589347A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6451415B1 (en) * | 1998-08-19 | 2002-09-17 | The Trustees Of Princeton University | Organic photosensitive optoelectronic device with an exciton blocking layer |
| US6333458B1 (en) * | 1999-11-26 | 2001-12-25 | The Trustees Of Princeton University | Highly efficient multiple reflection photosensitive optoelectronic device with optical concentrator |
Non-Patent Citations (3)
| Title |
|---|
| Novel Photovoltaic Devices Based on Donor-AcceptorMolecular and Condcuting Polymer Systems.IEEE TRANSACTIONS ON ELECTRON DEVICES44 8.1997,44(8),1315-1324. |
| Novel Photovoltaic Devices Based on Donor-AcceptorMolecular and Condcuting Polymer Systems.IEEE TRANSACTIONS ON ELECTRON DEVICES44 8.1997,44(8),1315-1324. * |
| 同上.44(8),1315-1324. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2589347A1 (en) | 2006-06-08 |
| EP1817800A1 (en) | 2007-08-15 |
| AU2004325239A1 (en) | 2006-06-08 |
| CN101120458A (en) | 2008-02-06 |
| MX2007006651A (en) | 2008-10-24 |
| JP2008522428A (en) | 2008-06-26 |
| WO2006060017A1 (en) | 2006-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7592539B2 (en) | Solid state photosensitive devices which employ isolated photosynthetic complexes | |
| US8987589B2 (en) | Architectures and criteria for the design of high efficiency organic photovoltaic cells | |
| US7314773B2 (en) | Low resistance thin film organic solar cell electrodes | |
| JP5118041B2 (en) | Encapsulated electrodes for organic devices | |
| CN101120458B (en) | Solid state photosensitive device using isolated photosynthetic complexes | |
| CA2627992A1 (en) | Organic photovoltaic cells utilizing ultrathin sensitizing layer | |
| KR20110060956A (en) | Organic tandem solar cells | |
| US10978654B2 (en) | Exciton management in organic photovoltaic multi-donor energy cascades | |
| WO2014085639A1 (en) | Hybrid planar-graded heterojunction for organic photovoltaics | |
| JP2004165516A (en) | Organic solar cell | |
| US20110030771A1 (en) | Organic photosensitive optoelectronic device with near-infrared sensitivity | |
| KR20150037974A (en) | Multijunction organic photovoltaics incorporating solution and vacuum deposited active layers | |
| AU2013347855A1 (en) | Hybrid planar-mixed heterojunction for organic photovoltaics | |
| Lin et al. | Self-Assembled Monolayer for Low-Power-Consumption, Long-Term-Stability, and High-Efficiency Quantum Dot Light-Emitting Diodes | |
| JP2004356229A (en) | Organic photoelectric conversion device | |
| KR20070103376A (en) | Solid state photosensitive devices which employ isolated photosynthetic complexes | |
| Das | Photovoltaic devices using photosynthetic protein complexes | |
| JP2014077042A (en) | Organic thin film solar cell material including dibenzopyrromethene compound | |
| Baldo et al. | Photosynthetic Photovoltaic Cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101006 Termination date: 20161202 |