CN107359050B - fluorescence resonance energy transfer light anode and preparation method thereof - Google Patents
fluorescence resonance energy transfer light anode and preparation method thereof Download PDFInfo
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- CN107359050B CN107359050B CN201710569389.5A CN201710569389A CN107359050B CN 107359050 B CN107359050 B CN 107359050B CN 201710569389 A CN201710569389 A CN 201710569389A CN 107359050 B CN107359050 B CN 107359050B
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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 25
- 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
- 239000002243 precursor Substances 0.000 claims description 44
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000005864 Sulphur Substances 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
- 239000007789 gas Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 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
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- VZOZFNFGWCBNFE-UHFFFAOYSA-N 3-iodopropane-1-thiol Chemical compound SCCCI VZOZFNFGWCBNFE-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 239000002253 acid Substances 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- APTGPWJUOYMUCE-UHFFFAOYSA-N S-Ethyl thioacetate Chemical compound CCSC(C)=O APTGPWJUOYMUCE-UHFFFAOYSA-N 0.000 claims description 2
- SBWFWBJCYMBZEY-UHFFFAOYSA-N S-Propyl thioacetate Chemical compound CCCSC(C)=O SBWFWBJCYMBZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 229910052793 cadmium Inorganic materials 0.000 claims 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 2
- 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
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 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 39
- 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
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 230000005611 electricity Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 113
- 239000000243 solution Substances 0.000 description 94
- 239000000975 dye Substances 0.000 description 47
- 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
- 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 18
- -1 propylthio Chemical group 0.000 description 17
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 12
- 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 12
- 239000012530 fluid Substances 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
- 230000000694 effects Effects 0.000 description 8
- 239000004020 conductor Substances 0.000 description 6
- 239000012792 core layer Substances 0.000 description 6
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 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
- 239000000980 acid dye Substances 0.000 description 3
- 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
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000013019 agitation Methods 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
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OHAHAVAHPNYWQR-UHFFFAOYSA-N C(CCCC)OC(CI)=S Chemical compound C(CCCC)OC(CI)=S OHAHAVAHPNYWQR-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 239000003153 chemical reaction reagent Substances 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
- 238000007654 immersion Methods 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
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propyl mercaptan Natural products CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 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
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000002791 soaking 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
- 125000000446 sulfanediyl group Chemical group *S* 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 fluorescence resonance energy transfer 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 is efficient, transferring efficiency of fluorescence resonance energy and electricity conversion are high.Method include the n-type semiconductor film for being deposited on conductive substrate is sensitized in squaraine dye alcoholic solution, flow back in the toluene solution of halogenated thiacetate it is halogenated after hydrolysis, 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 2~12h of the toluene soak semiconductor optical anode.It is easy to operate, controllability is good, at low cost.
Description
Technical field
The present invention relates to light anode technical field, in particular to a kind of fluorescence resonance energy transfer light anode and its
Preparation method.
Background technology
Energy crisis is increasingly serious, and sensitization solar battery is simple for process with its, the serial advantage such as of low cost becomes new
The research hotspot of energy field.However, the limited spectral response range of photosensitizer makes battery extinction imitate 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.
Currently, in relation to quantum dot and light-sensitive coloring agent fluorescence resonance energy transfer (FRET) bonding systemType electricity
The research in pond is still rare.It is in the prior artType battery is primarily present problems with：First, squaraine dye absorbs
For spectrum within the scope of 600~700nm, solar energy effective rate of utilization is low；Second is that excitation state electronics is multiple from dyestuff to quantum dot
The phenomenon that conjunction, weakens FRET efficiency and battery efficiency between the two；Kamat goes out band propylthio by four step chemical reactive synthesis
The squaraine dye of alcohol bridge chain is connect with quantum dot, and reaction step is more, reaction is complex；It is dye that it, which is by propyl mercaptan bridge chain,
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 so that the FRET energy transfer efficiencies between quantum dot and sensitizing dyestuff are limited, leads to light sun
Extinction efficiency and the photoelectric efficiency of battery be not high.
Invention content
The purpose of the present invention is to provide a kind of fluorescence resonance energy transfer light anode, have spectral response range it is wide,
The advantages that extinction is efficient, transferring efficiency of fluorescence resonance energy is high, electricity conversion is high between dyestuff and quantum dot.
Another object of the present invention is to provide a kind of preparation method of fluorescence resonance energy transfer light anode, operation letters
Just, at low cost, applied widely, light anode extinction efficiency obtained and electricity conversion are high.
What the embodiment of the present invention was realized in：
A kind of fluorescence resonance energy transfer light anode comprising conductive substrate, the n-type semiconductor film for being adsorbed in conductive substrate
And be adsorbed in the photoelectricity transmission layer of n-type semiconductor film, photoelectricity transmission layer include the squaraine dye for being connected to n-type semiconductor film,
It is connected to the halogenated thiols of squaraine dye and is connected to I type nuclear shell structure quantum point of 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 fluorescence resonance energy transfer light anode comprising partly lead the N-shaped for being deposited on conductive substrate
Body film is sensitized in the alcoholic solution of squaraine dye, and flow back halogenated rear hydrolysis in the toluene solution of halogenated thiacetate, must connect
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 toluene soak to connect
It is connected to 2~12h of semiconductor optical anode of function bridge chain molecule.
The advantageous effect of the embodiment of the present invention is：
Fluorescence resonance energy transfer 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 fluorescence resonance energy transfer
Energy acceptor.Spectral response range is wide, extinction is efficient.
Halogenated thiols are bonded with energy donor and energy acceptor respectively as function bridge chain molecule, make energy donor phase
Energy donor is uniformly distributed, the exciton ratio of generation fluorescence resonance energy transfer is made to improve；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 higher than the lumo energy of energy acceptor, can effectively inhibit the non-effective charge recombination between energy acceptor and energy donor, from
And enhance energy transfer effect between the two, transferring efficiency of fluorescence resonance energy height, photoelectric conversion between dyestuff and quantum dot
It is efficient.
The preparation method of fluorescence resonance energy transfer light anode provided by the invention.First by the n-type semiconductor film side of being dipped in
The alcoholic solution of acid dye makes the carboxyl of squaraine dye be bonded with n-type semiconductor film and is adsorbed in its surface, it is quick to obtain squaraine dye
The semiconductor optical anode of change.Halogenated thiacetate is used as connection energy donor in the function bridge chain molecule forerunner of energy acceptor
Body is dipped in the operation to flow back in the toluene solution of halogenated thiacetate, and the halogen end of halogenated thiacetate is made to be contaminated with side's acid
Halogenating reaction occurs for the hydrogen atom of secondary amine on the indole ring of material, obtains connecting the i.e. halogenated thio second of functional bridge chain molecular precursor
The semiconductor optical anode of acid esters.Hydrolysis makes function bridge chain molecular precursor generate the function bridge chain molecule that end carries sulfydryl, uses
It is bonded in quantum dot.
The shell conduction band positions of I type nucleocapsid 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, make the electronics transfer between dyestuff and quantum dot
It is 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
Fluorescence resonance energy transfer is enhanced.ZnS shells can be between Reasonable Regulation And Control energy donor and energy acceptor spacing, to
Enhance the efficiency of fluorescence resonance energy transfer between the two.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the structure and energy transfer schematic diagram of fluorescence resonance energy transfer light anode provided in an embodiment of the present invention；
Fig. 2 is the level structure schematic diagram of fluorescence resonance energy transfer 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 of quantum dot stratum nucleare schemes；
Fig. 4 is the CuInS that the embodiment of the present invention 1 provides2The TEM of@ZnS quantum dots schemes；
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 fluorescence resonance energy transfer light anodes.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Fluorescence resonance energy transfer light anode of the embodiment of the present invention and preparation method thereof is specifically described below.
Referring to Fig. 1, a kind of fluorescence resonance energy transfer light anode includes：Conductive substrate, the N-shaped 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 the side for being connected to 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, and squaraine dye is made to be adsorbed in n-type semiconductor film.
Further, squaraine dye is selected from In one kind.The absorption bands of SQ1, SQ2, SQ3, SQ4 and SQ5 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, halogenated sulphur
The sulfydryl of alcohol is bonded with I type nuclear shell structure quantum point.Halogenated thiols as function bridge chain molecule respectively with energy donor, that is, quantum
Point and energy acceptor, that is, squaraine dye are bonded, and energy donor is made to be evenly distributed relative to energy donor, prevent from supplying because of energy
Stronger electronics transfer effect or contact, which are quenched, between body and energy acceptor causes a large amount of of energy donor exciton to decay to make
The exciton ratio that fluorescence resonance energy transfer occurs declines, and helps to improve the efficiency of fluorescence resonance energy transfer.
The one kind of halogenated thiols in 2- iodos ethanethio, 3- iodo propyl mercaptan or 5- iodo amyl mercaptans,
Bonding action is good, operation is convenient.
Referring to Fig. 2, I type nuclear shell structure quantum point refers to the quantum of the conduction band positions of shell higher than the conduction band positions of stratum nucleare
Point can effectively absorb the nonabsorbable short wavelength's sunlight of energy acceptor 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, the I type nuclear shell structure quantum point using shell conduction band positions higher than the lumo energy of squaraine dye, again
Since 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 leading due to quantum dot
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 inhibit the non-effective charge recombination between energy acceptor and energy donor, enhances fluorescence between energy donor and energy acceptor
The ratio of Resonance energy transfer, 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, absorption spectrum are generally 350~620nm, and the wider and response range with squaraine dye of response range 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 fluorescence resonance energy transfer light anode, including the n-type semiconductor of conductive substrate will be deposited on
Film is sensitized in the alcoholic solution of squaraine dye, and flow back halogenated rear hydrolysis in the toluene solution of halogenated 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 divided with functional bridge chain is connect
The semiconductor optical anode bonding of son.
N-type semiconductor film is impregnated with the alcoholic solution of squaraine dye, the carboxyl of squaraine dye is made to be bonded with n-type semiconductor film,
So that squaraine dye is adsorbed in n-type semiconductor film and obtains the semiconductor optical anode of squaraine dye sensitization.
The alcoholic solution of the squaraine dye be the alcoholic solution containing SQ1, SQ2, SQ3, SQ4 or SQ5, spectral response range compared with
It is wide.Preferably the alcoholic solution be ethanol solution, a concentration of the 3 × 10 of squaraine dye-4~1 × 10-3Mol/L, it is convenient to prepare,
Reaction is controllable.
Soaking time is preferably advisable with 12~48h, will be deposited on before impregnating the n-type semiconductor film of conductive substrate in 80~
0.5~2h is heated under the conditions of 100 DEG C, adsorption effect is preferable.After the completion of absorption, by the semiconductor optical anode of squaraine dye sensitization
With ethyl alcohol, preferably rinsed with absolute ethyl alcohol after dry up, to remove the squaraine dye of n-type semiconductor film surface physical absorption, make
Halogenated 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 halogenated thiacetate to halogenated, the side that flows back
Halogenating reaction occurs for the hydrogen atom of secondary amine and the halogen end of halogenated thiacetate on the indole ring of acid dye, obtains connecting active
The semiconductor optical anode of energy bridge chain molecular precursor.
Halogenated thiacetate refers to the thiacetate of Halogen group elements, as the presoma of 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 mercaptan, 5-
Iodo amyl mercaptan.
Preferably, in the toluene solution of halogenated thiacetate halogenated thiacetate a concentration of 0.02~1mol/L.
Reflux temperature is 20~60 DEG C, and return time is 8~16h.Further, reflux operation carries out under the protection of inert gas,
Inert gas can be at least one of inert gas such as helium, neon, argon gas, Krypton, xenon or radon gas in the narrow sense,
Can be the lower gas of the reactivities such as nitrogen.Preferably, adopting nitrogen or argon gas in an embodiment of the present invention.Reaction is completed
Afterwards, the surface that the semiconductor optical anode of functional bridge chain molecular precursor is connected with toluene rinse removes remaining reactant.
The function bridge chain molecular precursor hydrolysis that hydrolysis operation after halogenating reaction is used to be connected to squaraine dye makes it
End generates the function bridge chain molecule that end carries 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 substance be added ethyl alcohol in adjust pH to 8~10.Hydrolysis preferably carries out under room 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 0.3~2h of quantum dot shell precursor solution reaction and obtains I type nuclear shell structure quantum point in the Surface Creation shell of stratum nucleare.
Further, quantum dot stratum nucleare forerunner is added with the speed of 0.1~0.3mL/min in quantum dot shell precursor solution
In liquid solution, growth obtains shell structurre character more preferably.
The shell that the reaction of quantum dot shell precursor solution generates is the broadbands ZnS 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 amount obtained
Son point is I type nucleocapsid quantum.
Quantum dot stratum nucleare precursor solution is better selected from CuInS2It is a kind of in@ZnS, CdS@ZnS or CdSe@ZnS
Stratum nucleare precursor solution, quantum dot spectral response range that growth obtains is high with squaraine dye matching degree, it is easy to operate, react
Controllability is good.
CuInS2The stratum nucleare precursor solution of@ZnS is optionally the 1- lauryl mercaptan solution containing indium acetate and cuprous iodide.
Further, a concentration of 0.2mol/L of indium acetate, a concentration of 0.2mol/L of cuprous iodide.
The stratum nucleare precursor solution of CdSe@ZnS is optionally containing cadmium acetate, octadecylamine, selenium powder and tributylphosphine
1- octadecylene solution.Further, it is the 1- ten of a concentration of 0.07mol/L of cadmium acetate, a concentration of 0.9mol/L of octadecylamine
The mixed liquor of eight alkene solution and the 1- octadecylene solution of a concentration of 1mol/L of selenium powder, a concentration of 0.2mol/L of tributylphosphine.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.
The stratum nucleare precursor solution of CdS@ZnS is optionally the 1- octadecylene solution containing cadmium acetate and sulphur simple substance.Further
Ground, the 1- octadecylene solution of a concentration of 0.1mol/L of the 1- octadecylenes solution and sulphur simple substance that are a concentration of 0.2mol/L of cadmium acetate
Mixed liquor.When mixing, after the 1- octadecylene solution containing cadmium acetate and sulphur simple substance is heated to about 200 DEG C of constant temperature 0.5h, Xiang Qi
It is rapidly added the 1- octadecylene solution containing sulphur simple substance.
Since target product is to generate the quantum dot of the shell containing ZnS, therefore significantly quantum dot shell precursor solution is energy
Generate the system of ZnS shells.Optionally, quantum dot shell precursor solution is the 1- containing zinc oleate, sulphur simple substance and tri octyl phosphine
Octadecylene solution.Further, a concentration of 0.1mol/L of zinc oleate, a concentration of 0.1mol/L of sulphur simple substance, tri octyl phosphine
A concentration of 9 × 10-4mol/L。
Aforesaid operations can effectively control the size of shell, make the absorption bands of quantum dot obtained be generally 350~
620nm, emission band is generally 620~800nm, high with the spectral region matching degree of squaraine dye, to enhance system
Spectral response range.It grows to obtain the ZnS shells for the broad-band gap that thickness is 2~10nm, conduction level position on stratum nucleare surface
Higher than squaraine dye lumo energy, inhibit the non-effective charge recombination between quantum dot and squaraine dye, inhibit squaraine dye with
Non-effective charge recombination between quantum dot；Regulate and control energy donor in the distance between energy acceptor.
I type nucleocapsid quantum is bonded concrete operations with the semiconductor optical anode for connecting functional bridge chain molecule：I type core
Core-shell structure quantum dots are scattered in toluene, impregnate the 2~12h of semiconductor optical anode for connecting 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 ethyl alcohol are preferably used successively
It rinses and dries up, toluene obtains fluorescence resonance energy transfer for removing extra quantum dot, ethyl alcohol for removing remaining toluene
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-shaped TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ1 while hot
A concentration of 3 × 10-412h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ1 sensitizations
Conductor light anode.
B. 2- iodo ethyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 2- iodo ethyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ1 sensitizations, nitrogen protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the presoma semiconductor optical anode of functional bridge chain molecule.
C. the presoma semiconductor optical anode for connecting functional bridge chain molecule is immersed in ethyl alcohol, pH to 8 is adjusted with KOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, 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 surface grows 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, is rinsed with ethyl alcohol, and drying obtains CuInS2@ZnS-SQ1 fluorescence
Resonance energy transfer light anode.
Embodiment 2
A. the porous N-shaped 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 a concentration of 6 × 10-4It is impregnated for 24 hours in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain SQ1 sensitizations
Semiconductor optical anode.
B. 3- iodo propyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 3- iodo propyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ1 sensitizations, nitrogen protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the semiconductor optical anode of functional bridge chain molecular precursor.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, 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 the rate of addition of 0.3mL/min to
It is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-418 weak solutions of 1- of mol/L tri octyl phosphines, constant temperature
0.3h, in CuInS2Stratum nucleare surface grows 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, is rinsed with ethyl alcohol, and drying obtains CuInS2@ZnS-SQ1 fluorescence
Resonance energy transfer light anode.
Embodiment 3
A. the porous N-shaped 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 a concentration of 3 × 10-418h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain SQ1 sensitizations
Semiconductor optical anode.
B. 2- iodo ethyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 2- iodo ethyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ1 sensitizations, argon gas protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the presoma semiconductor optical anode of functional bridge chain molecule.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, 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 the rate of addition of 0.2mL/min to its
It is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-418 weak solutions of 1- of mol/L tri octyl phosphines, constant temperature
2h, in CuInS2Stratum nucleare surface grows 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, is rinsed with ethyl alcohol, and drying obtains CuInS2@ZnS-SQ1 fluorescence
Resonance energy transfer light anode.
Embodiment 4
A. the porous N-shaped TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ5 while hot
A concentration of 1 × 10-312h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ5 sensitizations
Conductor light anode.
B. 3- iodo propyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.1mol/L of 3- iodo propyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ5 sensitizations, argon gas protection, constant temperature back flow reaction 10h under the conditions of 40 DEG C.It takes out
Toluene rinse is used in combination, dries 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 ethyl alcohol, pH to 9 is adjusted with KOH,
Normal-temperature reaction 1h.It takes out and is rinsed with ethyl alcohol, 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 the rate of addition of 0.2mL/min to its
It is slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-418 weak solutions of 1- of mol/L tri octyl phosphines, constant temperature
2h, in CuInS2Stratum nucleare surface grows 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, is rinsed with ethyl alcohol, and drying obtains CuInS2@ZnS-SQ5 fluorescence
Resonance energy transfer light anode.
Embodiment 5
A. the porous N-shaped TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ1 while hot
A concentration of 3 × 10-4It is impregnated for 24 hours in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ1 sensitizations
Conductor light anode.
B. 2- iodo ethyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 2- iodo ethyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ1 sensitizations, nitrogen protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the semiconductor optical anode of functional bridge chain molecular precursor.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with KOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. 18 weak solutions of 1- containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
It is slowly injected into 18 weak solutions of 1- containing 1mol/L selenium powders and 0.2mol/L tributylphosphines thereto, 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, is rinsed with ethyl alcohol, and drying obtains CdSe@ZnS-SQ1 fluorescence resonances
Energy transfer light anode.
Embodiment 6
A. the porous N-shaped 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 a concentration of 1 × 10-3It is impregnated for 24 hours in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain SQ5 sensitizations
Semiconductor optical anode.
B. 3- iodo propyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.08mol/L of 3- iodo propyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ5 sensitizations, nitrogen protection, constant temperature back flow reaction 12h under the conditions of 40 DEG C.It takes out
Toluene rinse is used in combination, dries 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 ethyl alcohol, pH to 10 is adjusted with KOH,
Normal-temperature reaction 1.5h.It takes out and is rinsed with ethyl alcohol, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. 18 weak solutions of 1- containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
It is slowly injected into 18 weak solutions of 1- containing 1mol/L selenium powders and 0.2mol/L tributylphosphines thereto, 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, is rinsed with ethyl alcohol, and drying obtains CdSe@ZnS-SQ5 fluorescence resonances
Energy transfer light anode.
Embodiment 7
A. the porous N-shaped TiO2 films being deposited in transparent conduction base sheet are heated into 1h at 95 DEG C, is immediately placed in SQ2 while hot
A concentration of 9 × 10-420h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ2 sensitizations
Conductor light anode.
B. 5- iodo thioacetic acid pentyl esters are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 5- iodo thioacetic acid pentyl esters
Toluene solution.Immerse the semiconductor optical anode of SQ2 sensitizations, nitrogen protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the semiconductor optical anode of functional bridge chain molecular precursor.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with KOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. 18 weak solutions of 1- containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
It is slowly injected into 18 weak solutions of 1- containing 1mol/L selenium powders and 0.2mol/L tributylphosphines thereto, 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 be slowly dropped into zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10 to 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, is rinsed with ethyl alcohol, and drying obtains CdSe@ZnS-SQ2 fluorescence resonances
Energy transfer light anode.
Embodiment 8
A. the porous N-shaped 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 a concentration of 3 × 10-418h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain SQ1 sensitizations
Semiconductor optical anode.
B. 2- iodo ethyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 2- iodo ethyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ1 sensitizations, argon gas protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the semiconductor optical anode of functional bridge chain molecular precursor.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. 18 weak solutions of 1- containing 0.07mol/L cadmium acetates and 0.9mol/L octadecylamines are heated to 270 DEG C,
It is slowly injected into 18 weak solutions of 1- containing 1mol/L selenium powders and 0.2mol/L tributylphosphines thereto, 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, is rinsed with ethyl alcohol, and drying obtains CdSe@ZnS-SQ1 fluorescence resonances
Energy transfer light anode.
Embodiment 9
A. the porous N-shaped TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ1 while hot
A concentration of 3 × 10-412h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ1 sensitizations
Conductor light anode.
B. 2- iodo ethyl thioacetates are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 2- iodo ethyl thioacetates
Toluene solution.Immerse the semiconductor optical anode of SQ1 sensitizations, argon gas protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the semiconductor optical anode of functional bridge chain molecular precursor.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. 18 weak solutions of 1- containing 0.2mol/L cadmium acetates are heated to 200 DEG C and constant temperature under agitation
0.5h injects rapidly 18 weak solutions of 1- containing 0.1mol/L sulphur powders thereto, and 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 it with the rate of addition of 0.1mL/min
Instill zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-418 weak solutions of 1- 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, is rinsed with ethyl alcohol, and drying obtains CdS@ZnS-SQ1 fluorescence resonance energy
Amount transfer light anode.
Embodiment 10
A. the porous N-shaped TiO2 films being deposited in transparent conduction base sheet are heated into 2h at 80 DEG C, is immediately placed in SQ5 while hot
A concentration of 3 × 10-412h is impregnated in the ethanol solution of mol/L.It takes out and is rinsed with absolute ethyl alcohol, dried up, obtain the half of SQ5 sensitizations
Conductor light anode.
B. 5- iodo thioacetic acid pentyl esters are dissolved in into toluene and is configured to a concentration of 0.02mol/L of 5- iodo thioacetic acid pentyl esters
Toluene solution.Immerse the semiconductor optical anode of SQ5 sensitizations, argon gas protection, constant temperature back flow reaction 8h under the conditions of 20 DEG C.It takes out simultaneously
With toluene rinse, drying must connect the semiconductor optical anode of functional bridge chain molecular precursor.
C. the semiconductor optical anode for connecting functional bridge chain molecular precursor is immersed in ethyl alcohol, pH to 8 is adjusted with NaOH,
Normal-temperature reaction 0.5h.It takes out and is rinsed with ethyl alcohol, dry up, the semiconductor optical anode of functional bridge chain molecule must be connected.
D. 18 weak solutions of 1- containing 0.2mol/L cadmium acetates are heated to 200 DEG C and constant temperature under agitation
0.5h injects rapidly 18 weak solutions of 1- containing 0.1mol/L sulphur powders thereto, and 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 it with the rate of addition of 0.1mL/min
Instill zinc oleate containing 0.1mol/L, 0.1mol/L sulphur and 9 × 10-418 weak solutions of 1- 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, is rinsed with ethyl alcohol, and drying obtains CdS@ZnS-SQ5 fluorescence resonance energy
Amount transfer light anode.
To in the size of quantum dot and spectrum property made from embodiment 1-10 and light anode between quantum dot and dyestuff
Transferring efficiency of fluorescence resonance energy tested, the results are shown in Table 1.
1. spectrum test of table
According to the data of table 1, in conjunction with Fig. 5 and Fig. 6, light anode and squaraine dye matching degree made from the embodiment of the present invention
Height, transferring efficiency of fluorescence resonance energy are high.
In conclusion the preparation method of the fluorescence resonance energy transfer light anode of the embodiment of the present invention is easy to operate, controllable
Property is good, at low cost, and fluorescence resonance energy transfer light anode spectral response range obtained is wide, extinction is efficient, dyestuff and quantum
Transferring efficiency of fluorescence resonance energy height, electricity conversion are high between point.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range 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 without creative efforts
Other embodiment shall fall within the protection scope of the present invention.
Claims (18)
1. a kind of fluorescence resonance energy transfer light anode, which is characterized 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, which is characterized in that the squaraine dye is selected from In one kind, the I type nuclear shell structure quantum point be selected from CuInS2@
One kind in ZnS, CdS@ZnS or CdSe@ZnS.
3. light anode according to claim 1, which is characterized in that the halogenated thiols are selected from 2- iodos ethanethio, 3-
One kind in iodo propyl mercaptan or 5- iodo amyl mercaptans.
4. a kind of preparation method of fluorescence resonance energy transfer light anode, which is characterized in that including：Conductive substrate will be deposited on
N-type semiconductor film is sensitized in the alcoholic solution of squaraine dye, and flow back halogenated rear water in the toluene solution of halogenated thiacetate
Solution, 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 first
Benzene impregnates 2~12h of semiconductor optical anode of the functional bridge chain molecule of connection.
5. preparation method according to claim 4, which is characterized 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 is added quantum dot shell precursor solution under the conditions of being 210~250 DEG C and reacts 0.3~2h.
6. preparation method according to claim 5, which is characterized in that the quantum dot shell precursor solution with 0.1~
The speed of 0.3mL/min is added in the quantum dot stratum nucleare precursor solution.
7. preparation method according to claim 5, which is characterized 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.
8. preparation method according to claim 5, which is characterized 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.
9. preparation method according to claim 8, which is characterized in that the quantum dot stratum nucleare precursor solution is containing acetic acid
The 1- lauryl mercaptan solution of indium and cuprous iodide.
10. preparation method according to claim 8, which is characterized in that the quantum dot stratum nucleare precursor solution is containing second
The 1- octadecylene solution of sour cadmium, octadecylamine, selenium powder and tributylphosphine.
11. preparation method according to claim 8, which is characterized in that the quantum dot stratum nucleare precursor solution is containing second
The 1- octadecylene solution of sour cadmium and sulphur simple substance.
12. preparation method according to claim 4, which is characterized in that the squaraine dye is selected from In one kind.
13. preparation method according to claim 12, which is characterized in that side's acid described in the alcoholic solution of the squaraine dye
A concentration of the 3 × 10 of dyestuff-4~1 × 10-3mol/L。
14. preparation method according to claim 4, which is characterized in that the halogenated thiacetate is selected from iodo containing 2-
One kind in ethyl thioacetate, 3- iodos propyl thioacetate or 5- iodo thioacetic acid pentyl esters.
15. preparation method according to claim 14, which is characterized in that in the toluene solution of the halogenated thiacetate
A concentration of 0.02~1mol/L of the halogenated thiacetate.
16. preparation method according to claim 4, which is characterized in that the return time of the reflux is 8~16h, reflux
Temperature is 20~60 DEG C.
17. preparation method according to claim 16, which is characterized in that the reflux carries out under inert gas shielding.
18. preparation method according to claim 17, which is characterized in that the inert gas is nitrogen or argon gas.
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