CN107359050A - FRET light anode and preparation method thereof - Google Patents
FRET light anode and preparation method thereof Download PDFInfo
- Publication number
- CN107359050A CN107359050A CN201710569389.5A CN201710569389A CN107359050A CN 107359050 A CN107359050 A CN 107359050A CN 201710569389 A CN201710569389 A CN 201710569389A CN 107359050 A CN107359050 A CN 107359050A
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- quantum dot
- anode
- squaraine dye
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- 238000002866 fluorescence resonance energy transfer Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 195
- 239000004065 semiconductor Substances 0.000 claims abstract description 97
- 239000002096 quantum dot Substances 0.000 claims abstract description 80
- 230000003287 optical effect Effects 0.000 claims abstract description 72
- IHXWECHPYNPJRR-UHFFFAOYSA-N 3-hydroxycyclobut-2-en-1-one Chemical compound OC1=CC(=O)C1 IHXWECHPYNPJRR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003573 thiols Chemical class 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 10
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 230000005622 photoelectricity Effects 0.000 claims abstract description 8
- 239000000975 dye Substances 0.000 claims description 55
- 239000002243 precursor Substances 0.000 claims description 42
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 239000005864 Sulphur Substances 0.000 claims description 22
- -1 iodo propyl group Chemical group 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 8
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 7
- 239000011258 core-shell material Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000980 acid dye Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- XDSKMOFKLKJGFB-UHFFFAOYSA-N 5-iodopentane-1-thiol Chemical class SCCCCCI XDSKMOFKLKJGFB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- SBWFWBJCYMBZEY-UHFFFAOYSA-N S-Propyl thioacetate Chemical compound CCCSC(C)=O SBWFWBJCYMBZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 150000002168 ethanoic acid esters Chemical class 0.000 claims 1
- 125000002346 iodo group Chemical group I* 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 230000004044 response Effects 0.000 abstract description 15
- 230000003595 spectral effect Effects 0.000 abstract description 13
- 230000008033 biological extinction Effects 0.000 abstract description 8
- 230000005611 electricity Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 2
- 125000001475 halogen functional group Chemical group 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 107
- 239000000243 solution Substances 0.000 description 93
- 235000019441 ethanol Nutrition 0.000 description 47
- 206010070834 Sensitisation Diseases 0.000 description 24
- 230000008313 sensitization Effects 0.000 description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 238000011010 flushing procedure Methods 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000001035 drying Methods 0.000 description 12
- 239000012530 fluid Substances 0.000 description 11
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- SWMBQMGPRYJSCI-UHFFFAOYSA-N octylphosphane Chemical class CCCCCCCCP SWMBQMGPRYJSCI-UHFFFAOYSA-N 0.000 description 10
- 230000006870 function Effects 0.000 description 9
- 239000004020 conductor Substances 0.000 description 6
- 239000012792 core layer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 150000004694 iodide salts Chemical class 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- SGJUCMOYVKXLDY-UHFFFAOYSA-N acetic acid;cadmium Chemical group [Cd].CC(O)=O.CC(O)=O SGJUCMOYVKXLDY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- ZJGSVSYBKAZJGP-KVVVOXFISA-N (z)-octadec-9-enoic acid;zinc Chemical compound [Zn].CCCCCCCC\C=C/CCCCCCCC(O)=O ZJGSVSYBKAZJGP-KVVVOXFISA-N 0.000 description 1
- OHAHAVAHPNYWQR-UHFFFAOYSA-N C(CCCC)OC(CI)=S Chemical compound C(CCCC)OC(CI)=S OHAHAVAHPNYWQR-UHFFFAOYSA-N 0.000 description 1
- APTGPWJUOYMUCE-UHFFFAOYSA-N S-Ethyl thioacetate Chemical compound CCSC(C)=O APTGPWJUOYMUCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002165 resonance energy transfer Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of FRET light anode and preparation method thereof, belongs to light anode technical field.Light anode containing conductive substrate, be adsorbed in the n-type semiconductor film of the substrate and be adsorbed in the photoelectricity transmission layer of the semiconductor film, photoelectricity transmission layer, which contains, to be connected to the squaraine dye of the semiconductor film, is connected to the halogenated thiols of squaraine dye and is connected to I type nuclear shell structure quantum point of halogenated thiols, and the shell conduction band positions of the quantum dot are higher than the lumo energy of squaraine dye.Spectral response range is wide, extinction efficiency high, transferring efficiency of fluorescence resonance energy and electricity conversion are high.Method includes the n-type semiconductor film for being deposited on conductive substrate being sensitized in squaraine dye alcoholic solution, hydrolyzed after the halo that flowed back in the toluene solution of halo thiacetate, must connect the semiconductor optical anode of functional bridge chain molecule；I type nuclear shell structure quantum point of the shell containing ZnS is scattered in 2~12h of the toluene soak semiconductor optical anode.It is simple to operate, controllability is good, cost is low.
Description
Technical field
The present invention relates to light anode technical field, in particular to a kind of FRET light anode and its
Preparation method.
Background technology
Energy crisis is increasingly serious, and so that its technique is simple, cost is cheap etc., serial advantage turns into new to sensitization solar battery
The study hotspot of energy field.However, the limited spectral response range of sensitising agent imitates battery extinction in sensitization solar battery
Rate is restricted, and leverages the photoelectric efficiency of battery.Therefore, the spectral response range of solar cell, structure are effectively expanded
The stronger wide spectrum response type battery of extinction efficiency is built, for improving the electricity conversion of battery and promoting its practicalization
For it is significant.
At present, about quantum dot and light-sensitive coloring agent FRET (FRET) bonding systemType electricity
The research in pond is still rare.It is of the prior artType battery is primarily present problems with：First, squaraine dye absorbs
For spectrum in the range of 600~700nm, solar energy effective rate of utilization is low；Second, excitation state electronics is answered from dyestuff to quantum dot
The phenomenon of conjunction weakens FRET efficiency and the battery efficiency between the two；Kamat goes out band propylthio by four step chemical reactive synthesis
The squaraine dye of alcohol bridge chain is connected with quantum dot, and reactions steps are more, reaction is complex；It is by propyl group mercaptan bridge chain for dye
Material and quantum dot provide the spacing condition needed for FRET effects, and the compliance of the bridge chain and strand crimp make spacing control
System becomes difficult.Factors above causes the FRET energy transfer efficiencies between quantum dot and sensitizing dyestuff to be limited, and causes light sun
Extinction efficiency and the photoelectric efficiency of battery be not high.
The content of the invention
It is an object of the invention to provide a kind of FRET light anode, it possess spectral response range it is wide,
The advantages that transferring efficiency of fluorescence resonance energy is high between extinction efficiency high, dyestuff and quantum dot, electricity conversion is high.
Another object of the present invention is to provide a kind of preparation method of FRET light anode, operation letter
Just, cost is low, applied widely, and obtained light anode extinction efficiency and electricity conversion are high.
What embodiments of the invention were realized in：
A kind of FRET light anode, it includes conductive substrate, is adsorbed in the n-type semiconductor film of conductive substrate
And be adsorbed in the photoelectricity transmission layer of n-type semiconductor film, photoelectricity transmission layer include be connected to n-type semiconductor film squaraine dye,
The halogenated thiols for being connected to squaraine dye and the I type nuclear shell structure quantum point for being connected to halogenated thiols, I type nuclear shell structure quantum point
Shell conduction band positions be higher than squaraine dye lumo energy.
A kind of preparation method of FRET light anode, it includes partly leading the n-type for being deposited on conductive substrate
Body film is sensitized in the alcoholic solution of squaraine dye, is hydrolyzed, must be connected after the halo that flowed back in the toluene solution of halo thiacetate
It is connected to the semiconductor optical anode of function bridge chain molecule；I type nuclear shell structure quantum point of the shell containing ZnS is scattered in into toluene soak to connect
It is connected to 2~12h of semiconductor optical anode of function bridge chain molecule.
The beneficial effect of the embodiment of the present invention is：
FRET light anode provided by the invention, I type nuclear shell structure quantum point can as energy donor
The nonabsorbable near infrared light of energy acceptor squaraine dye is effectively absorbed, then is transferred energy to by FRET
Energy acceptor.Spectral response range is wide, extinction efficiency high.
Halogenated thiols are bonded with energy donor and energy acceptor respectively as function bridge chain molecule, make energy donor phase
It is uniformly distributed for energy donor, improves the exciton ratio of generation FRET；I type nuclear shell structure quantum point
Shell can be between Reasonable Regulation And Control energy donor and energy acceptor spacing, between energy donor and energy acceptor dipole effect
Enhancing, transferring efficiency of fluorescence resonance energy improve.The shell conduction band positions of I type nuclear shell structure quantum point are higher than stratum nucleare conduction band positions
And it is higher than the lumo energy of energy acceptor, it can effectively suppress the non-effective charge recombination between energy acceptor and energy donor, from
And strengthen energy transfer effect therebetween, transferring efficiency of fluorescence resonance energy height, photoelectric conversion between dyestuff and quantum dot
Efficiency high.
The preparation method of FRET light anode provided by the invention.First by the n-type semiconductor film side of being dipped in
The alcoholic solution of acid dye, the carboxyl of squaraine dye is bonded with n-type semiconductor film and be adsorbed in its surface, it is quick to obtain squaraine dye
The semiconductor optical anode of change.Halo thiacetate is used as connection energy donor in the function bridge chain molecule forerunner of energy acceptor
Body, the operation to be flowed back in the toluene solution of halo thiacetate is dipped in, the halogen end and side's acid for making halo thiacetate contaminate
Halogenating reaction occurs for the hydrogen atom of secondary amine on the indole ring of material, obtains connecting the functional bridge chain molecular precursor i.e. thio second of halo
The semiconductor optical anode of acid esters.Hydrolysis makes function bridge chain molecular precursor generation end carry the function bridge chain molecule of sulfydryl, uses
It is bonded in quantum dot.
The shell conduction band positions of I type core shell structure quantum of the shell containing ZnS be higher than squaraine dye lumo energy, and due to
The shell conduction band positions of I type nuclear shell structure quantum point are higher than stratum nucleare conduction band positions, shift the electronics between dyestuff and quantum dot
Obstructed with the ZnS shells of composite quilt broad-band gap, the electronics transfer between dyestuff and quantum dot is weakened, and is vied each other therewith
FRET is enhanced.ZnS shells can be between Reasonable Regulation And Control energy donor and energy acceptor spacing, so as to
Strengthen the efficiency of FRET therebetween.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the structure and energy transfer schematic diagram of FRET light anode provided in an embodiment of the present invention；
Fig. 2 is the level structure schematic diagram of FRET light anode provided in an embodiment of the present invention；
Fig. 3 is the CuInS that the embodiment of the present invention 1 provides2The TEM figures of quantum dot stratum nucleare；
Fig. 4 is the CuInS that the embodiment of the present invention 1 provides2The TEM figures of@ZnS quantum dots；
Fig. 5 is the CuInS that the embodiment of the present invention 1 provides2The spectrogram of@ZnS quantum dots and SQ1；
Fig. 6 is the CuInS that the embodiment of the present invention 1 provides2The spectrogram of@ZnS-SQ1 FRET light anodes.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase
Product.
FRET light anode of the embodiment of the present invention and preparation method thereof is specifically described below.
Referring to Fig. 1, a kind of FRET light anode includes：Conductive substrate, the n-type for being adsorbed in conductive substrate
Semiconductor film and the photoelectricity transmission layer for being adsorbed in n-type semiconductor film, photoelectricity transmission layer include being connected to the side of n-type semiconductor film
Acid dye, the halogenated thiols for being connected to squaraine dye and the I type nuclear shell structure quantum point for being connected to halogenated thiols.
The carboxyl of squaraine dye is bonded with n-type semiconductor film, squaraine dye is adsorbed in n-type semiconductor film.
Further, squaraine dye is selected from In one kind.SQ1, SQ2, SQ3, SQ4 and SQ5 absorption bands are 550~800nm, and spectral response range is wider.
The secondary amine of squaraine dye is bonded with the halogen of halogenated thiols, and halogenated thiols refer to the mercaptan of Halogen group elements, halo sulphur
The sulfydryl of alcohol is bonded with I type nuclear shell structure quantum point.Halogenated thiols are respectively quantum with energy donor as function bridge chain molecule
Point and energy acceptor are that squaraine dye is bonded, and energy donor is evenly distributed relative to energy donor, are prevented because energy supplies
Between body and energy acceptor stronger electronics transferance or contact a large amount of decay for causing energy donor exciton are quenched so that
The exciton ratio that FRET occurs declines, and is favorably improved the efficiency of FRET.
The one kind of halogenated thiols in 2- iodos ethanethio, 3- iodo propyl group mercaptan or 5- iodo amyl mercaptans, its
Bonding action is good, operation is convenient.
Referring to Fig. 2, I type nuclear shell structure quantum point refers to quantum of the conduction band positions higher than the conduction band positions of stratum nucleare of shell
Point, it can effectively absorb the nonabsorbable short wavelength's sunshine of energy acceptor institute as energy donor, then pass through fluorescence resonance
Energy transfer transfers energy to energy acceptor.The spectral response range of light anode is set to be expanded, spectral response range is wide, inhales
Light efficiency is high.The shell of I type nuclear shell structure quantum point can spacing of the Reasonable Regulation And Control energy donor between energy acceptor, enhancing
Dipole effect of the energy donor between energy acceptor, transferring efficiency of fluorescence resonance energy improve.
Further, I type nuclear shell structure quantum point of the lumo energy of squaraine dye is higher than using shell conduction band positions, again
Because the conduction band positions of the shell of I type nuclear shell structure quantum point are higher than the conduction band positions of stratum nucleare, can avoid because quantum dot is led
With energy level less than excitation state electronics caused by squaraine dye lumo energy from energy acceptor to the compound phenomenon of energy donor, energy
Effectively suppress the non-effective charge recombination between energy acceptor and energy donor, strengthen fluorescence between energy donor and energy acceptor
The ratio of Resonance energy transfer, so as to effectively improve electricity conversion.
In preferred embodiments of the present invention, I type nuclear shell structure quantum point is selected from CuInS2@ZnS, CdS@ZnS or CdSe@
One kind in ZnS, its absorption spectrum are generally 350~620nm, and response range is wider and response range with squaraine dye is mutual
It is good to mend effect；The absorption spectrum matching degree of emission spectrum and squaraine dye is high；The growth operation of shell and stratum nucleare simplicity, reaction can
Control.
A kind of preparation method of FRET light anode, including the n-type semiconductor that conductive substrate will be deposited on
Film is sensitized in the alcoholic solution of squaraine dye, is hydrolyzed, must be connected after the halo that flowed back in the toluene solution of halo thiacetate
The semiconductor optical anode of functional bridge chain molecule；By I type nuclear shell structure quantum point of the shell containing ZnS with being connected functional bridge chain point
The semiconductor optical anode bonding of son.
N-type semiconductor film is soaked with the alcoholic solution of squaraine dye, the carboxyl of squaraine dye is bonded with n-type semiconductor film,
Squaraine dye is adsorbed in n-type semiconductor film and obtain the semiconductor optical anode of squaraine dye sensitization.
The alcoholic solution of the squaraine dye is the alcoholic solution containing SQ1, SQ2, SQ3, SQ4 or SQ5, its spectral response range compared with
It is wide.Preferably the alcoholic solution is ethanol solution, and the concentration of squaraine dye is 3 × 10-4~1 × 10-3Mol/L, it is convenient that it is prepared,
React controllable.
Soak time is preferably advisable with 12~48h, will be deposited on before immersion the n-type semiconductor film of conductive substrate in 80~
0.5~2h is heated under the conditions of 100 DEG C, its adsorption effect is preferable.After the completion of absorption, by the semiconductor optical anode of squaraine dye sensitization
With ethanol, preferably rinsed with absolute ethyl alcohol after dry up, with remove n-type semiconductor film surface physics absorption squaraine dye, make
Halo thiacetate can be effectively bonded with the squaraine dye for being bonded to n-type semiconductor film.
The semiconductor optical anode that squaraine dye is sensitized is dipped in the toluene solution of halo thiacetate the halo that flows back, side
Halogenating reaction occurs for the halogen end of the hydrogen atom of secondary amine and halo thiacetate on the indole ring of acid dye, obtains connecting active
The semiconductor optical anode of energy bridge chain molecular precursor.
Halo thiacetate refers to the thiacetate of Halogen group elements, its presoma as halogenated thiols, for controlling
Brewed brine element carries out halogenating reaction with squaraine dye.It is selected from 2- iodos ethyl thioacetate, 3- iodos propyl thioacetate or 5-
A kind of in iodo thioacetic acid pentyl ester, i.e., corresponding halogenated thiols are followed successively by 2- iodos ethanethio, 3- iodo propyl group mercaptan, 5-
Iodo amyl mercaptan.
It is preferred that the concentration of halo thiacetate is 0.02~1mol/L in the toluene solution of halo thiacetate.
Reflux temperature is 20~60 DEG C, and return time is 8~16h.Further, reflux operation is carried out under the protection of inert gas,
Inert gas can be inert gas such as at least one of helium, neon, argon gas, Krypton, xenon or radon gas in the narrow sense,
Can be the relatively low gas of the reactivities such as nitrogen.It is preferred that nitrogen or argon gas are adopted in an embodiment of the present invention.Reaction is completed
Afterwards, the surface of the semiconductor optical anode of functional bridge chain molecular precursor is connected with toluene rinse, removes remnants reactant.
Hydrolysis operation after halogenating reaction is used to the function bridge chain molecular precursor hydrolysis for being connected to squaraine dye making it
End generation end carries the function bridge chain molecule of sulfydryl, for being bonded with quantum dot.
Hydrolysis operation preferably use pH for 8~10 alkali alcosol, such as by potassium hydroxide, sodium hydroxide alkali or alkali
Property material add ethanol in adjust pH to 8~10.Hydrolysis is preferably carried out under normal temperature, and the reaction time is 0.5~2h.
The concrete operations of I type nuclear shell structure quantum point for growing the shell containing ZnS are：By quantum dot stratum nucleare precursor solution in
0.25~12h is heated under the conditions of 210~350 DEG C to grow to obtain stratum nucleare.Holding fluid temperature drips under the conditions of being about 210~250 DEG C
Enter quantum dot shell precursor solution and react 0.3~2h, in the Surface Creation shell of stratum nucleare, obtain I type nuclear shell structure quantum point.
Further, quantum dot shell precursor solution adds quantum dot stratum nucleare forerunner with 0.1~0.3mL/min speed
In liquid solution, its growth obtains shell structurre character more preferably.
The shell of quantum dot shell precursor solution reaction generation is ZnS broadbands shell, therefore the quantum used in the reaction
Point stratum nucleare precursor solution should be the system that stratum nucleare conduction level is less than ZnS shell conduction levels, make aforesaid operations are obtained to measure
Son point is I type core shell structure quantum.
Quantum dot stratum nucleare precursor solution is preferably selected from CuInS2It is a kind of in@ZnS, CdS@ZnS or CdSe@ZnS
Stratum nucleare precursor solution, it grows, and obtained quantum dot spectral response range is high, easy to operate with squaraine dye matching degree, reaction
Controllability is good.
CuInS2@ZnS stratum nucleare precursor solution is optionally the 1- lauryl mercaptan solution containing indium acetate and cuprous iodide.
Further, the concentration of indium acetate is 0.2mol/L, and the concentration of cuprous iodide is 0.2mol/L.
CdSe@ZnS stratum nucleare precursor solution is optionally containing cadmium acetate, octadecylamine, selenium powder and tributylphosphine
1- octadecylene solution.Further, it is acetic acid cadmium concentration is 0.07mol/L, octadecylamine concentration is 0.9mol/L 1- ten
The mixed liquor of eight alkene solution and selenium powder concentration is 1mol/L, tributylphosphine concentration is 0.2mol/L 1- octadecylene solution.Mixing
When, the 1- octadecylene solution containing cadmium acetate and octadecylamine is heated to about 270 DEG C of backward its and is slowly injected into containing selenium powder and three
The 1- octadecylene solution of butyl phosphine.
CdS@ZnS stratum nucleare precursor solution is optionally the 1- octadecylene solution containing cadmium acetate and sulphur simple substance.Further
Ground, it is the 1- octadecylene solution that the concentration of 1- octadecylenes solution that acetic acid cadmium concentration is 0.2mol/L and sulphur simple substance is 0.1mol/L
Mixed liquor.During mixing, after the 1- octadecylene solution containing cadmium acetate and sulphur simple substance is heated to about into 200 DEG C of constant temperature 0.5h, Xiang Qi
It is rapidly added the 1- octadecylene solution containing sulphur simple substance.
Because target product is the quantum dot of generation shell containing ZnS, therefore significantly quantum dot shell precursor solution is energy
Generate the system of ZnS shells.Alternatively, quantum dot shell precursor solution is the 1- containing zinc oleate, sulphur simple substance and tri octyl phosphine
Octadecylene solution.Further, oleic acid zinc concentration is 0.1mol/L, and the concentration of sulphur simple substance is 0.1mol/L, tri octyl phosphine
Concentration is 9 × 10-4mol/L。
Aforesaid operations can effectively control the size of shell, make the absorption bands of obtained quantum dot generally for 350~
620nm, emission band are generally 620~800nm, high with the spectral region matching degree of squaraine dye, so as to strengthen system
Spectral response range.The ZnS shells for the broad-band gap that thickness is 2~10nm, its conduction level position are obtained in stratum nucleare superficial growth
Higher than squaraine dye lumo energy, suppress the non-effective charge recombination between quantum dot and squaraine dye, suppress squaraine dye with
Non-effective charge recombination between quantum dot；Regulate and control energy donor in the distance between energy acceptor.
I type core shell structure quantum be connected functional bridge chain molecule semiconductor optical anode be bonded concrete operations be：I type core
Core-shell structure quantum dots are scattered in toluene, and immersion connects 2~12h of semiconductor optical anode of functional bridge chain molecule, and connection is active
The sulfydryl of the semiconductor optical anode of energy bridge chain molecule is bonded with quantum dot.After the completion of immersion, toluene and ethanol are preferably used successively
Rinse and dry up, toluene is used to remove unnecessary quantum dot, and ethanol is used for the toluene for removing residual, obtains FRET
Light anode.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ1 while hot
Concentration is 3 × 10-412h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ1 sensitizations
Conductor light anode.
B. it is 0.02mol/L 2- iodo ethyl thioacetates to be dissolved in toluene to be configured to 2- iodo ethyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ1 sensitizations is immersed, nitrogen is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the presoma semiconductor optical anode of functional bridge chain molecule must be connected.
C. the presoma semiconductor optical anode for connecting functional bridge chain molecule is immersed in ethanol, pH to 8 is adjusted with KOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the 1- lauryl mercaptans solution of indium acetate containing 0.2mol/L and 0.2mol/L cuprous iodides is added under the conditions of 210 DEG C
Hot 0.25h, growth obtain CuInS2Quantum dot stratum nucleare, as shown in Figure 3.It is 210 DEG C to maintain fluid temperature, with 0.1mL/min's
Rate of addition instills zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10 to it-4The 1- 18 of mol/L tri octyl phosphines is dilute molten
Liquid, constant temperature 0.3h, in CuInS2Stratum nucleare superficial growth ZnS shells.Obtain CuInS2@ZnS quantum dots, as shown in Figure 4.
E. by CuInS2@ZnS quantum dots, which are dispersed in toluene, is configured to uniform quantum dot solution, and it is functional to immerse connection
The semiconductor optical anode 2h of bridge chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CuInS2@ZnS-SQ1 fluorescence
Resonance energy transfer light anode.
Embodiment 2
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 0.5h at 100 DEG C, be immediately placed in while hot
SQ1 concentration is 6 × 10-424h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain SQ1 sensitizations
Semiconductor optical anode.
B. it is 0.02mol/L 3- iodo propyl thioacetates to be dissolved in toluene to be configured to 3- iodo propyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ1 sensitizations is immersed, nitrogen is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the 1- lauryl mercaptans solution of indium acetate containing 0.2mol/L and 0.2mol/L cuprous iodides is added under the conditions of 210 DEG C
Hot 0.25h, growth obtain CuInS2Quantum dot stratum nucleare.Maintain fluid temperature be 230 DEG C, with 0.3mL/min rate of addition to
It is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-4The weak solutions of 1- 18 of mol/L tri octyl phosphines, constant temperature
0.3h, in CuInS2Stratum nucleare superficial growth ZnS shells.Obtain CuInS2@ZnS quantum dots.
E. by CuInS2@ZnS quantum dots, which are dispersed in toluene, is configured to uniform quantum dot solution, and it is functional to immerse connection
The semiconductor optical anode 2h of bridge chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CuInS2@ZnS-SQ1 fluorescence
Resonance energy transfer light anode.
Embodiment 3
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 1.5h at 90 DEG C, be immediately placed in while hot
SQ1 concentration is 3 × 10-418h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain SQ1 sensitizations
Semiconductor optical anode.
B. it is 0.02mol/L 2- iodo ethyl thioacetates to be dissolved in toluene to be configured to 2- iodo ethyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ1 sensitizations is immersed, argon gas is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the presoma semiconductor optical anode of functional bridge chain molecule must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the 1- lauryl mercaptans solution of indium acetate containing 0.2mol/L and 0.2mol/L cuprous iodides is added under the conditions of 210 DEG C
Hot 12h, growth obtain CuInS2Quantum dot stratum nucleare.Maintain fluid temperature be 220 DEG C, with 0.2mL/min rate of addition to its
It is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-4The weak solutions of 1- 18 of mol/L tri octyl phosphines, constant temperature
2h, in CuInS2Stratum nucleare superficial growth ZnS shells.Obtain CuInS2@ZnS quantum dots.
E. by CuInS2@ZnS quantum dots, which are dispersed in toluene, is configured to uniform quantum dot solution, and it is functional to immerse connection
The semiconductor optical anode 2h of bridge chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CuInS2@ZnS-SQ1 fluorescence
Resonance energy transfer light anode.
Embodiment 4
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ5 while hot
Concentration is 1 × 10-312h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ5 sensitizations
Conductor light anode.
B. it is 0.1mol/L 3- iodo propyl thioacetates to be dissolved in toluene to be configured to 3- iodo propyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ5 sensitizations is immersed, argon gas is protected, constant temperature back flow reaction 10h under the conditions of 40 DEG C.Take out
And with toluene rinse, drying, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 9 is adjusted with KOH,
Normal-temperature reaction 1h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the 1- lauryl mercaptans solution of indium acetate containing 0.2mol/L and 0.2mol/L cuprous iodides is added under the conditions of 210 DEG C
Hot 12h, growth obtain CuInS2Quantum dot stratum nucleare.Maintain fluid temperature be 250 DEG C, with 0.2mL/min rate of addition to its
It is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-4The weak solutions of 1- 18 of mol/L tri octyl phosphines, constant temperature
2h, in CuInS2Stratum nucleare superficial growth ZnS shells.Obtain CuInS2@ZnS quantum dots.
E. by CuInS2@ZnS quantum dots, which are dispersed in toluene, is configured to uniform quantum dot solution, and it is functional to immerse connection
The semiconductor optical anode 6h of bridge chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CuInS2@ZnS-SQ5 fluorescence
Resonance energy transfer light anode.
Embodiment 5
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ1 while hot
Concentration is 3 × 10-424h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ1 sensitizations
Conductor light anode.
B. it is 0.02mol/L 2- iodo ethyl thioacetates to be dissolved in toluene to be configured to 2- iodo ethyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ1 sensitizations is immersed, nitrogen is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with KOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the weak solutions of 1- 18 containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
The weak solutions of 1- 18 containing 1mol/L selenium powders and 0.2mol/L tributylphosphines are slowly injected into thereto, and above-mentioned mixed liquor is existed
0.25h is heated under the conditions of 250 DEG C, growth obtains CdSe quantum dot stratum nucleare.It is 210 DEG C to maintain fluid temperature, with 0.1mL/min's
Rate of addition is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10 to it-4The 1- 18 of mol/L tri octyl phosphines
Weak solution, constant temperature 0.3h, grow ZnS shells in CdSe core layer surface.Obtain CdSe@ZnS quantum dots.
E. CdSe ZnS quantum dots are dispersed in toluene and are configured to uniform quantum dot solution, immersed and connect functional bridge
The semiconductor optical anode 2h of chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CdSe@ZnS-SQ1 fluorescence resonances
Energy transfer light anode.
Embodiment 6
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 0.5h at 100 DEG C, be immediately placed in while hot
SQ5 concentration is 1 × 10-324h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain SQ5 sensitizations
Semiconductor optical anode.
B. it is 0.08mol/L 3- iodo propyl thioacetates to be dissolved in toluene to be configured to 3- iodo propyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ5 sensitizations is immersed, nitrogen is protected, constant temperature back flow reaction 12h under the conditions of 40 DEG C.Take out
And with toluene rinse, drying, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 10 is adjusted with KOH,
Normal-temperature reaction 1.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the weak solutions of 1- 18 containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
The weak solutions of 1- 18 containing 1mol/L selenium powders and 0.2mol/L tributylphosphines are slowly injected into thereto, and above-mentioned mixed liquor is existed
0.5h is heated under the conditions of 250 DEG C, growth obtains CdSe quantum dot stratum nucleare.It is 210 DEG C to maintain fluid temperature, with 0.15mL/min's
Rate of addition is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10 to it-4The 1- 18 of mol/L tri octyl phosphines
Weak solution, constant temperature 1h, grow ZnS shells in CdSe core layer surface.Obtain CdSe@ZnS quantum dots.
E. CdSe ZnS quantum dots are dispersed in toluene and are configured to uniform quantum dot solution, immersed and connect functional bridge
The semiconductor optical anode 8h of chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CdSe@ZnS-SQ5 fluorescence resonances
Energy transfer light anode.
Embodiment 7
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 1h at 95 DEG C, is immediately placed in SQ2 while hot
Concentration is 9 × 10-420h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ2 sensitizations
Conductor light anode.
B. it is 0.02mol/L 5- iodo thioacetic acid pentyl esters to be dissolved in toluene to be configured to 5- iodo thioacetic acid pentyl ester concentration
Toluene solution.The semiconductor optical anode of SQ2 sensitizations is immersed, nitrogen is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with KOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the weak solutions of 1- 18 containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
The weak solutions of 1- 18 containing 1mol/L selenium powders and 0.2mol/L tributylphosphines are slowly injected into thereto, and above-mentioned mixed liquor is existed
0.25h is heated under the conditions of 250 DEG C, growth obtains CdSe quantum dot stratum nucleare.It is 210 DEG C to maintain fluid temperature, with 0.25mL/min
Rate of addition zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10 are slowly dropped into it-4The 1- ten of mol/L tri octyl phosphines
Eight weak solutions, constant temperature 2h, grow ZnS shells in CdSe core layer surface.Obtain CdSe@ZnS quantum dots.
E. CdSe ZnS quantum dots are dispersed in toluene and are configured to uniform quantum dot solution, immersed and connect functional bridge
The semiconductor optical anode 2h of chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CdSe@ZnS-SQ2 fluorescence resonances
Energy transfer light anode.
Embodiment 8
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 1.5h at 90 DEG C, be immediately placed in while hot
SQ1 concentration is 3 × 10-418h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain SQ1 sensitizations
Semiconductor optical anode.
B. it is 0.02mol/L 2- iodo ethyl thioacetates to be dissolved in toluene to be configured to 2- iodo ethyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ1 sensitizations is immersed, argon gas is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the weak solutions of 1- 18 containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
The weak solutions of 1- 18 containing 1mol/L selenium powders and 0.2mol/L tributylphosphines are slowly injected into thereto, and above-mentioned mixed liquor is existed
0.25h is heated under the conditions of 250 DEG C, growth obtains CdSe quantum dot stratum nucleare.It is 250 DEG C to maintain fluid temperature, with 0.2mL/min's
Rate of addition is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10 to it-4The 1- 18 of mol/L tri octyl phosphines
Weak solution, constant temperature 2h, grow ZnS shells in CdSe core layer surface.Obtain CdSe@ZnS quantum dots.
E. CdSe ZnS quantum dots are dispersed in toluene and are configured to uniform quantum dot solution, immersed and connect functional bridge
The semiconductor optical anode 2h of chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CdSe@ZnS-SQ1 fluorescence resonances
Energy transfer light anode.
Embodiment 9
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ1 while hot
Concentration is 3 × 10-412h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ1 sensitizations
Conductor light anode.
B. it is 0.02mol/L 2- iodo ethyl thioacetates to be dissolved in toluene to be configured to 2- iodo ethyl thioacetates concentration
Toluene solution.The semiconductor optical anode of SQ1 sensitizations is immersed, argon gas is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the weak solutions of 1- 18 containing 0.2mol/L cadmium acetates are heated to 200 DEG C and constant temperature under agitation
0.5h, inject the weak solutions of 1- 18 containing 0.1mol/L sulphur powders rapidly thereto, above-mentioned mixed liquor is added under the conditions of 250 DEG C
Hot 1h, growth obtain CdS quantum dot stratum nucleare.It is 210 DEG C to maintain fluid temperature, slow to its with 0.1mL/min rate of addition
Instill zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-4The weak solutions of 1- 18 of mol/L tri octyl phosphines, constant temperature 0.3h,
ZnS shells are grown in CdS core layer surface.Obtain CdS@ZnS quantum dots.
E. CdS ZnS quantum dots are dispersed in toluene and are configured to uniform quantum dot solution, immersed and connect functional bridge
The semiconductor optical anode 2h of chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CdS@ZnS-SQ1 fluorescence resonance energy
Amount transfer light anode.
Embodiment 10
A. the porous n-type TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ5 while hot
Concentration is 3 × 10-412h is impregnated in mol/L ethanol solution.Take out and rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ5 sensitizations
Conductor light anode.
B. it is 0.02mol/L 5- iodo thioacetic acid pentyl esters to be dissolved in toluene to be configured to 5- iodo thioacetic acid pentyl ester concentration
Toluene solution.The semiconductor optical anode of SQ5 sensitizations is immersed, argon gas is protected, constant temperature back flow reaction 8h under the conditions of 20 DEG C.Take out simultaneously
With toluene rinse, dry up, the semiconductor optical anode of functional bridge chain molecular precursor must be connected.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethanol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.Take out and use alcohol flushing, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. the weak solutions of 1- 18 containing 0.2mol/L cadmium acetates are heated to 200 DEG C and constant temperature under agitation
0.5h, inject the weak solutions of 1- 18 containing 0.1mol/L sulphur powders rapidly thereto, above-mentioned mixed liquor is added under the conditions of 250 DEG C
Hot 1h, growth obtain CdS quantum dot stratum nucleare.It is 250 DEG C to maintain fluid temperature, slow to its with 0.1mL/min rate of addition
Instill zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-4The weak solutions of 1- 18 of mol/L tri octyl phosphines, constant temperature 2h,
CdS core layer surface grows ZnS shells.Obtain CdS@ZnS quantum dots.
E. CdS ZnS quantum dots are dispersed in toluene and are configured to uniform quantum dot solution, immersed and connect functional bridge
The semiconductor optical anode 2h of chain molecule.Taking-up toluene rinse, with alcohol flushing, drying, obtain CdS@ZnS-SQ5 fluorescence resonance energy
Amount transfer light anode.
To in the size of quantum dot made from embodiment 1-10 and spectrum property, and light anode between quantum dot and dyestuff
Transferring efficiency of fluorescence resonance energy tested, as a result as shown in table 1.
The spectrum test of table 1.
According to the data of table 1, with reference to Fig. 5 and Fig. 6, light anode made from the embodiment of the present invention and squaraine dye matching degree
Height, transferring efficiency of fluorescence resonance energy are high.
In summary, the preparation method of the FRET light anode of the embodiment of the present invention is simple to operate, controllable
Property is good, cost is low, and obtained FRET light anode spectral response range is wide, extinction efficiency high, dyestuff and quantum
Transferring efficiency of fluorescence resonance energy height, electricity conversion are high between point.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Embodiment in the present invention, those of ordinary skill in the art are obtained all under the premise of creative work is not made
Other embodiment, belong to the scope of protection of the invention.
Claims (10)
1. a kind of FRET light anode, it is characterised in that including conductive substrate, be adsorbed in the conductive substrate
N-type semiconductor film and the photoelectricity transmission layer for being adsorbed in the n-type semiconductor film, the photoelectricity transmission layer are described including being connected to
The squaraine dye of n-type semiconductor film, the halogenated thiols for being connected to the squaraine dye and the I type core for being connected to the halogenated thiols
Core-shell structure quantum dots, the shell conduction band positions of the I type nuclear shell structure quantum point are higher than the lumo energy of the squaraine dye.
2. light anode according to claim 1, it is characterised in that the squaraine dye is selected from
In one kind, the I type nuclear shell structure quantum point is selected from CuInS2@
One kind in ZnS, CdS@ZnS or CdSe@ZnS.
3. light anode according to claim 1, it is characterised in that the halogenated thiols are selected from 2- iodos ethanethio, 3-
One kind in iodo propyl group mercaptan or 5- iodo amyl mercaptans.
A kind of 4. preparation method of FRET light anode, it is characterised in that including：Conductive substrate will be deposited on
N-type semiconductor film is sensitized in the alcoholic solution of squaraine dye, water after the halo that flowed back in the toluene solution of halo thiacetate
Solution, the semiconductor optical anode of functional bridge chain molecule must be connected；I type nuclear shell structure quantum point of the shell containing ZnS is scattered in first
2~12h of semiconductor optical anode of the benzene immersion functional bridge chain molecule of connection.
5. preparation method according to claim 4, it is characterised in that I type nuclear shell structure quantum point of the shell containing ZnS
It is made according to following operation：Quantum dot stratum nucleare precursor solution is heated into 0.25~12h under the conditions of 210~350 DEG C；Keep liquid
Temperature adds quantum dot shell precursor solution under the conditions of being 210~250 DEG C and reacts 0.3~2h；Alternatively, the quantum dot
Shell precursor solution is added in the quantum dot stratum nucleare precursor solution with 0.1~0.3mL/min speed.
6. preparation method according to claim 5, it is characterised in that institute's quantum dot shell precursor solution is containing oleic acid
The 1- octadecylene solution of zinc, sulphur simple substance and tri octyl phosphine.
7. preparation method according to claim 5, it is characterised in that the quantum dot stratum nucleare precursor solution is selected from
CuInS2A kind of stratum nucleare precursor solution in@ZnS, CdS@ZnS or CdSe@ZnS；Alternatively, before the quantum dot stratum nucleare
Drive liquid solution is the 1- lauryl mercaptan solution containing indium acetate and cuprous iodide；Alternatively, the quantum dot stratum nucleare precursor solution
For the 1- octadecylene solution containing cadmium acetate, octadecylamine, selenium powder and tributylphosphine；Alternatively, the quantum dot stratum nucleare forerunner
Liquid solution is the 1- octadecylene solution containing cadmium acetate and sulphur simple substance.
8. preparation method according to claim 4, it is characterised in that the squaraine dye is selected from
In one kind；Alternatively, side described in the alcoholic solution of the squaraine dye
The concentration of acid dye is 3 × 10-4~1 × 10-3mol/L。
9. preparation method according to claim 4, it is characterised in that the halo thiacetate is selected from the sulphur of iodo containing 2-
For one kind in ethyl acetate, 3- iodos propyl thioacetate or 5- iodo thioacetic acid pentyl esters；Alternatively, the halo is thio
The concentration of halo thiacetate described in the toluene solution of acetic acid esters is 0.02~1mol/L.
10. preparation method according to claim 4, it is characterised in that the return time of the backflow is 8~16h, backflow
Temperature is 20~60 DEG C；Alternatively, described flow back is carried out under inert gas shielding；Alternatively, the inert gas is nitrogen
Or argon gas.
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