CN109988556A - Quantum dot solid film and its preparation method and application - Google Patents
Quantum dot solid film and its preparation method and application Download PDFInfo
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- CN109988556A CN109988556A CN201711481898.9A CN201711481898A CN109988556A CN 109988556 A CN109988556 A CN 109988556A CN 201711481898 A CN201711481898 A CN 201711481898A CN 109988556 A CN109988556 A CN 109988556A
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- quantum dot
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 206
- 239000007787 solid Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims description 21
- -1 halide anions Chemical class 0.000 claims abstract description 125
- 238000012986 modification Methods 0.000 claims abstract description 30
- 230000004048 modification Effects 0.000 claims abstract description 29
- 150000004820 halides Chemical class 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims description 25
- 239000002798 polar solvent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- 238000002161 passivation Methods 0.000 abstract description 12
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- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 15
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- 239000002131 composite material Substances 0.000 description 7
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- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical group CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
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- 150000002500 ions Chemical class 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910004613 CdTe Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 3
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 238000004070 electrodeposition Methods 0.000 description 2
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- 230000005476 size effect Effects 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical group COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000795633 Olea <sea slug> Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- PJYXVICYYHGLSW-UHFFFAOYSA-J tetrachloroplumbane Chemical compound Cl[Pb](Cl)(Cl)Cl PJYXVICYYHGLSW-UHFFFAOYSA-J 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention provides a kind of quantum dot solid films, quantum dot in the quantum dot solid film is the quantum dot that halide anions and halide ion are passivated altogether, wherein, the halide anions modification is in the quantum dot surface, and the halide ion is in conjunction with the quantum dot that halide anions are modified.After the halide anions modify quantum dot, the cation vacancy for capableing of effectively less surface enhances surface passivation effect in turn, and the reduction of surface vacancy can reduce surface capture state, and the quantum solid film charge-conduction after halide passivation accordingly enhances.
Description
Technical field
The invention belongs to technical field of solar batteries more particularly to a kind of quantum dot solid film and preparation method thereof and answer
With.
Background technique
Quantum dot solar cell belongs to the third generation solar cell, while excellent characteristic enables its retainer member performance
The manufacturing cost of solar battery is greatly reduced, thus has become current one of forward position and hot subject.
For semiconductor material, when its particle size drops to it is suitable with its Exciton Bohr Radius when, will be present not
Continuous highest be occupied molecular orbit and it is minimum be not occupied molecular orbital energy level, and its energy gap reduces and continuous with partial size
It broadens, this phenomenon is referred to as quantum size effect.Quantum size effect can be such that quantum dot occurs in its absorption spectrum
One or more apparent exciton absorption peaks and the continuous blue shift with the reduction of quantum dot size, therefore change can be passed through
The size of quantum dot regulates and controls its optical absorption wavelength, so that having in the application of Colloidal Quantum Dots in solar cells
Unique advantage.Skin effect, another possessed distinguishing feature of nano material is large specific surface area, nanocrystalline size
Smaller, specific surface area is bigger, and the ratio that surface atom number accounts for whole atomicities is higher.With increasing for surface atom number, table
Face Atomic coordinate is insufficient, and unsaturated bond and dangling bonds increase, and surface is enable to increase sharply.Its surface atom is due to very high
Activity, it is highly unstable, it is easy in conjunction with other atoms.The a large amount of surface state defects in Colloidal Quantum Dots surface will affect its light
And electric property, and its huge surface can be brought to the preparation, preservation and use of quantum dot and its solar battery
Challenge.Currently, reduce quantum dot surface defect conventional manner be grow broad-band gap shell or surface covering it is longer
Ligand modify both modes, but the charge-conduction performance of quantum dot solid film that both modes obtain is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of quantum dot solid films and preparation method thereof, it is intended to solve Colloidal Quantum Dots and deposit
The problem of a large amount of surface state defects will affect its optics and electric property.
Another object of the present invention is to provide a kind of battery devices containing above-mentioned quantum dot solid film.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of quantum dot solid film, the quantum dot in the quantum dot solid film are that halide anions and halide ion are total
The quantum dot of passivation, wherein the halide anions modification is in the quantum dot surface, the halide ion and halide yin
The quantum dot of ion modification combines.
Correspondingly, a kind of preparation method of quantum dot solid film, comprising the following steps:
Halide is dispersed in polar solvent, halide anions are obtained, the polar solvent is that can make the halogen
Compound ionizes the organic solvent to form halide anions and halide cation；
Surface is provided and contains the quantum dot of oil-soluble ligand, by the quantum dot at the halide anions mixing
Exchange reaction occurs for the ligand of reason, the halide anions and the quantum dot surface, and halide anions are prepared and repair
The quantum dot of decorations；
The quantum dot that the halide anions modification is deposited on substrate, prepares prefabricated quantum dot solid film；
The prefabricated quantum dot solid film is mixed with halide ion, makes the prefabricated quantum dot solid film and halide ion
In conjunction with obtaining quantum dot solid film.
And a kind of battery device, including light absorbing layer, and the light absorbing layer is above-mentioned quantum dot solid film.
Quantum dot solid film provided by the invention, the quantum dot in the quantum dot solid film, be halide anions and
The quantum dot that halide ion is passivated altogether, wherein the halide anions modification is in the quantum dot surface, the halide ion
In conjunction with the quantum dot of halide anions modification.After the halide anions modify quantum dot, can effectively compared with
The cation vacancy on few surface enhances surface passivation effect in turn, and the reduction of surface vacancy can reduce surface capture state, halogenation
Quantum solid film charge-conduction after object passivation accordingly enhances (mainly since the distance between quantum dot and quantum dot drop
It is low).Further, the quantum dot that halide anions are modified further is passivated using halide ion, can be further decreased
The charge-conduction of surface defect and enhancing quantum dot solid film.The quantum dot solid film as characterized above, can drop
While low quantum dot surface defect, and the charge-conduction and stability of quantum dot solid film can be enhanced.
Quantum dot and the halogenation of oil-soluble ligand are contained in surface by the preparation method of quantum dot solid film provided by the invention
The mixing of object anion makes halide anions and oil-soluble ligand that ligand exchange occur, and then combines in quantum dot particle surface
Halide anions obtain the quantum dot of halide anions modification, the quantum spot deposition that the halide anions are modified
At prefabricated quantum dot solid film；The prefabricated quantum dot solid film is further passivated using halide ion, table is reinforced to quantum dot
Face passivation.While so that obtained quantum dot solid film can reduce quantum dot surface defect, and quantum solid point can be enhanced
The charge-conduction and stability of state film.This method is simple, easily operated, and repeatability is strong.
Therefore battery device provided by the invention, has preferable device efficiency containing above-mentioned quantum dot solid film.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of quantum dot solid film, the quantum dot in the quantum dot solid film is halide
The quantum dot that anion and halide ion are passivated altogether, wherein halide anions modification is described in the quantum dot surface
Halide ion is in conjunction with the quantum dot that halide anions are modified.
Quantum dot solid film provided in an embodiment of the present invention, the quantum dot in the quantum dot solid film are halide yin
The quantum dot that ion and halide ion are passivated altogether, wherein the halide anions modification is in the quantum dot surface, the halogen
Plain ion is in conjunction with the quantum dot that halide anions are modified.It, can after the halide anions modify quantum dot
The cation vacancy on effective less surface enhances surface passivation effect in turn, and the reduction of surface vacancy can reduce surface capture
State, the quantum solid film charge-conduction after halide passivation accordingly enhance (mainly due between quantum dot and quantum dot
Distance reduces).Further, the quantum dot that halide anions are modified further is passivated using halide ion, it can be into one
Step reduces surface defect and enhances the charge-conduction of quantum dot solid film.The quantum dot solid film as characterized above,
While can reduce quantum dot surface defect, and the charge-conduction and stability of quantum dot solid film can be enhanced.
Specifically, the selection of the quantum dot particle does not limit strictly in the embodiment of the present invention, can be selected from CdSe,
PbSe、PbS、PbSe/CdSe、PbS/CdS、AgS、HgS、CdTe、CdTe/CdS、CdTe/CdZnS、InP、InP/ZnS、InP/
ZnSeS.The launch wavelength range of above-mentioned quantum dot is in visible region.Further, the size model of the quantum dot particle
Enclose 1~10nm, the Bohr radius of the quantum dot (10~50nm, the value of the Bohr radius of quantum dot specifically correspond to it is above-mentioned not
Congener quantum dot, and discontinuous value) it is greater than the particle size of quantum dot.
The embodiment of the present invention is by making on quantum dot particle band in the quantum dot particle surface combination halide anions
Negative electricity, which can not only guarantee the fluorescence intensity of quantum dot, but also can reduce the reunion between quantum dot, so as to
The preparation of quantum dot composite membrane is realized by electro-deposition method.
Preferably, the halide anions that the quantum dot particle surface combines are [MXm+n]n-, wherein M be selected from Pb, Cd,
One of Zn, In, Fe, Sb, X are selected from one of Cl, Br, I, and m is the valence number of M, and n is the halide anions
Valence mumber.Wherein, m is 2 or 3, and when m is 2, n 1；When m is 3, n is 1 or 2.Specifically, Pb is in [MXm+n]n-In with Pb2+
Form exist, Cd is in [MXm+n]n-In with Cd2+Form exist, Zn is in [MXm+n]n-In with Zn2+Form exist, In exists
[MXm+n]n-In with In2+Form exist, Fe is in [MXm+n]n-In can be with Fe2+Form exist, can also be with Fe3+Form
In the presence of；Sb is in [MXm+n]n-In with Sb2+Form exist.
Above-mentioned preferred metal and halogen type can be in the higher polar solvents of dielectric constant after the halide of formation
It is middle to ionize, form halide anions and halide cation.Specifically, reaction equation are as follows:
Thus obtained halide anions, can the ligand effectively with the quantum dot swap, and the amount of being firmly bonded to
Son point particle surface, keeps quantum dot negatively charged.And the halide anions belong to L-type ligand, only with a metallic atom knot
Close, it can thus be avoided quantum dot particle and quantum dot particle are crosslinked, facilitate halide ion to quantum dot carry out into
The passivation of one step.
In the embodiment of the present invention, the halide ion is selected from Cl-、Br-、I-At least one of, preferably Cl-.The halogen
Plain ion can further decrease surface defect and enhance the charge-conduction of quantum dot solid film.
In the embodiment of the present invention, the quantum dot solid film with a thickness of 5-60nm.
Quantum dot solid film described in the embodiment of the present invention can be prepared by following methods.
Correspondingly, a kind of preparation method of quantum dot solid film, comprising the following steps:
S01. halide is dispersed in polar solvent, obtains halide anions, the polar solvent is can make institute
It states halide and ionizes the organic solvent to form halide anions and halide cation；
S02., the quantum dot for containing oil-soluble ligand in surface is provided, the quantum dot is mixed with the halide anions
Exchange reaction occurs for the ligand of processing, the halide anions and the quantum dot surface, and halide anions are prepared
The quantum dot of modification；
S03. the quantum dot that the halide anions modification is deposited on substrate, prepares prefabricated quantum dot solid film；
S04. the prefabricated quantum dot solid film is mixed with halide ion, makes the prefabricated quantum dot solid film and halogen
Ions binding obtains quantum dot solid film.
Surface, is contained the quantum dot of oil-soluble ligand by the preparation method of quantum dot solid film provided in an embodiment of the present invention
It is mixed with halide anions, makes halide anions and oil-soluble ligand that ligand exchange occur, and then in quantum dot particle table
Face combines halide anions, obtains the quantum dot of halide anions modification, the quantum that the halide anions are modified
Spot deposition is at prefabricated quantum dot solid film；The prefabricated quantum dot solid film is further passivated using halide ion, to quantum dot
Reinforce surface passivation.While so that obtained quantum dot solid film can reduce quantum dot surface defect, and being capable of the amount of enhancing
The charge-conduction and stability of son point solid film.This method is simple, easily operated, and repeatability is strong.
Specifically, the type selection of the halide anions is as described above in above-mentioned steps S01.Preferably, described
Halide is MXm, the halide anions are [MXm+n]n-, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Fe, Sb,
X is selected from one of Cl, Br, I, and m is the valence number of M, and n is the valence mumber of the halide anions, wherein and m is 2 or 3, and
When m is 2, n 1；When m is 3, n is 1 or 2.
For dispersing the polar solvent of the halide, can sufficiently to dissolve the halide, and make the halide
Ionization forms the organic solvent of halide anions and halide cation, i.e., with the organic solvent of high dielectric constant.It is excellent
Choosing, alms giver's number (DN) of the polar solvent is 10-50, to guarantee being adequately ionized for halide.In above-mentioned preferred feelings
On the basis of shape, boundary's electric constant of the polar solvent increases, and corresponding polarity also will increase, and electron donation is stronger, therefore energy
It is enough that the halide is preferably promoted to ionize.Specific preferred, the organic solvent is selected from methylformamide, propylene carbonic acid
At least one of ester, dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethyl alcohol, propyl alcohol are conducive to the halide hair
Raw ionization generates halide anions and halide cation.
In above-mentioned steps S02, the quantum dot that oil-soluble ligand is contained on surface is provided, wherein the oil-soluble ligand is selected from
At least one of oleic acid (OA), oleyl amine (OAm), trioctylphosphine phosphorus (TOP), trioctylphosphine oxygen phosphorus (TOPO).Above-mentioned oil-soluble ligand
Structure is R1-COOH、R2-NH2、R3-P、R4- P=O, wherein R1、R2、R3、R4Zwitterion for alkyl, with quantum dot particle
Binding ability it is weaker, when standing time is longer in air, be easy to fall off.Therefore, it is necessary to by the amount of the oil-soluble ligand
The surface ligand of son point is replaced.
The preparation method of the quantum dot containing oil-soluble ligand is prepared using conventional oily phase method.Contain by described in
There is the quantum dot of oil-soluble ligand to obtain quantum dot dispersion liquid using organic solvent dispersion.Preferably, it is selected from just with organic solvent
At least one of hexane, chloroform, chlorobenzene, toluene, but not limited to this.Preferred solvent is conducive to the evenly dispersed of quantum dot.
Preferably, the concentration of the quantum dot dispersion liquid is 10~60mg/ml, and excessive concentration is unfavorable for halide anions and carries out to it
Modification.
By the quantum dot and the halide anions mixed processing, the halide ionizes generation in polar solvent
Halide anions, can effectively be exchanged with the surface ligand of quantum dot, so with the metallic atom knot in quantum dot
It closes, and is securely adsorbed on quantum dot surface, keep the quantum dot surface negatively charged.By the quantum dot and halide yin
It is 100mg:(0.2 according to the quality molar ratio of the quantum dot and the halide anions in the step of Ar ion mixing processing
~1mmol) ratio mixed processing.The ratio of the suitable halide anions and the quantum dot, can make the halogen
Compound anion has suitable distribution density in the quantum dot, is conducive to quantum dot and sufficiently modifies.
The embodiment of the present invention prepares the quantum dot of halide anions modification, carries out in an inert atmosphere, reaction temperature is
30-60 DEG C, reaction time 1-10h.Further, by obtained halide anions modification quantum dot by precipitating reagent into
After row centrifuge separation, it is dried.The quantum dot of obtained halide anions modification, is preferably dispersed in methylformamide, third
In at least one of olefinic carbon acid esters, dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethyl alcohol, propyl alcohol, compound quantity is formed
Son point solution.
It include: to provide in the step of depositing the quantum dot of the halide anions modification on substrate in above-mentioned steps S03
The dispersion liquid of composite quantum dot, in the dispersion liquid of the composite quantum dot, composite quantum dot is the amount of halide anions modification
Sub-, the quantum dot of the halide anions modification includes quantum dot particle, and is incorporated in the quantum dot particle surface
Halide anions；The dispersion liquid of the composite quantum dot is deposited on substrate, is made annealing treatment, is obtained prefabricated quantum dot solid-state
Film.
Wherein, the concentration of the dispersion liquid of the composite quantum dot is preferably 5-30mg/ml.The substrate can be conventional
Substrate is also possible to deposit the function substrate of other materials.Deposition method of the embodiment of the present invention includes but is not limited to print, beat
Print, electro-deposition etc..Further, the substrate for the dispersion liquid for having deposited composite quantum dot is made annealing treatment, annealing
Temperature is 60-150 DEG C, time 30-60min.Preferred prefabricated quantum dot solid film with a thickness of 5-60nm.
In above-mentioned steps S04, in the step of prefabricated quantum dot solid film is mixed with halide ion, it is preferred that mention
For the solution containing halide ion, the prefabricated quantum dot solid film is immersed in the solution of the solution containing halide ion.
It is further preferred that providing halogen gas dissolution to halide ion solution in organic solvent.It is furthermore preferred that the halide ion
The concentration range of solution is 0.005~0.01mmol/ml, is conducive to halide ion and carries out adequately to prefabricated quantum dot solid film
Passivation improves the charge transport properties and stability of quantum dot solid film.The prefabricated quantum dot solid film is immersed in described
Time preferred unit 10-60min in halide ion solution, to promote halide ion to the abundant blunt of prefabricated quantum dot solid film
Change.
Further, the solid film obtained after halide ion is passivated is made annealing treatment, prepares fine and close quantum dot
Solid film.Preferably, the temperature of the annealing is 60-150 DEG C, time 30-60min.
And the embodiment of the invention provides a kind of battery devices, including light absorbing layer, and the light absorbing layer is above-mentioned
Quantum dot solid film.
Quantum dot in the quantum dot solid film is the quantum dot that halide anions and halide ion are passivated altogether,
In, the halide anions modification is in the quantum dot surface, the quantum of the halide ion and halide anions modification
Point combines.Preferably, the halide anions that the metal oxide nanoparticles surface combines are [MXm+n]n-, wherein M choosing
It is selected from one of Cl, Br, I from one of Pb, Cd, Zn, In, Fe, Sb, X, m is the valence number of M, and n is the halide
The valence mumber of anion.Wherein, m is 2 or 3, and when m is 2, n 1；When m is 3, n is 1 or 2.Specifically, Pb is in [MXm+n]n-
In with Pb2+Form exist, Cd is in [MXm+n]n-In with Cd2+Form exist, Zn is in [MXm+n]n-In with Zn2+Form deposit
In is in [MXm+n]n-In with In2+Form exist, Fe is in [MXm+n]n-In can be with Fe2+Form exist, can also be with Fe3 +Form exist；Sb is in [MXm+n]n-In with Sb2+Form exist.
It is illustrated combined with specific embodiments below.
Embodiment 1
A kind of preparation method of quantum dot solid film, comprising the following steps:
Preparing for S1.PbS quantum dot is as follows:
S11. plumbi oleas { Pb (OA)2Precursor preparation: take the lead acetate trihydrate of 0.6mmol, 2ml oleic acid (OA),
10ml 18 dilute (ODE) is added in three-necked flask, and first room temperature is vented 20min, and then temperature is increased to 150 DEG C of stirring 30min
Temperature is reduced to 120 DEG C afterwards.
S12. the preparation of sulphur (S) precursor: claim the S of 4mmol to be added in the trioctylphosphine oxygen phosphorus (TOP) of 6ml, be heated to
170 DEG C of maintenance 30min, then cool to 140 DEG C.
S13. after the mixeding liquid temperature in S11 being increased to 150 DEG C, sulphur (S) precursor of 2ml is taken to be rapidly injected flask
Interior reaction 10min, rapidly take out heating mantle liquid temperature to be mixed is cold go to room temperature after by addition extractant and precipitating reagent carry out
Centrifuge separation cleaning obtains oil-soluble PbS near-infrared quantum dots and is dried, then by dry oil-soluble quantum dot point
It is dispersed in the solution for being prepared into that concentration is 30mg/ml in n-hexane, the ligand on surface is oleic acid (OA).
S2.PbCl2The ligand preparation for exchanging PbS quantum surface is as follows:
S21. the PbCl of 0.5mmol is taken2It is dispersed in the methylformamide of 5ml, strong stirring is until PbCl2All dissolutions
It is spare.
S22. the PbS quantum 100mg prepared in S21 is taken to be dispersed in spare in the n-hexane of 3ml.
S23. the solution in S21 and S22 is mixed into stirring 3h strongly under an inert gas.
S24. precipitating reagent is added into S23, and dry be prepared containing PbCl is centrifuged3 -Or PbCl4 2-Modification
Quantum dot.
S3.PbCl2Preparing for modification PbS quantum solid film is as follows:
S31. the PbCl for taking 100mg above-mentioned steps S2 to prepare2The PbS quantum of modification is dispersed in the methyl formyl of 10ml
It is dissolved in amine spare.
S32. the PbCl prepared using S312The PbS quantum solution of modification prepares one layer of quantum by the way of printing
Point solid film.
S33. 80 DEG C of annealing 30min are used to the quantum dot solid film prepared.
S4. halide ion (Cl is utilized-) further passivation quantum dot solid film prepare it is as follows:
S41. the carbon tetrachloride solution of 10ml is taken, chlorine is then led into carbon tetrachloride solution until the solubility of chlorine is
It is spare to stop ventilation when 0.08mmol/ml.
S42. the quantum dot solid film prepared in above-mentioned S43 is immersed in the carbon tetrachloride solution containing chlorine and is impregnated
30min。
S43. the quantum dot solid film after immersion is then subjected to 80 DEG C of annealing 30min.
Embodiment 2
A kind of battery device, including light absorbing layer, and the light absorbing layer is quantum dot solid-state prepared by above-described embodiment 1
Film.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (11)
1. a kind of quantum dot solid film, which is characterized in that quantum dot in the quantum dot solid film be halide anions and
The quantum dot that halide ion is passivated altogether, wherein the halide anions modification is in the quantum dot surface, the halide ion
In conjunction with the quantum dot of halide anions modification.
2. quantum dot solid film as described in claim 1, which is characterized in that the halide anions are [MXm+n]n-,
In, M is selected from one of Pb, Cd, Zn, In, Fe, Fe, Sb, and X is selected from one of Cl, Br, I, and m is the valence number of M, and n is
The valence mumber of the halide anions, wherein m is 2 or 3, and when m is 2, n 1；When m is 3, n is 1 or 2.
3. quantum dot solid film as described in claim 1, which is characterized in that the halide ion is selected from Cl-、Br-、I-In
It is at least one.
4. quantum dot solid film as described in any one of claims 1-3, which is characterized in that the thickness of the quantum dot solid film
For 5-60nm.
5. a kind of preparation method of quantum dot solid film, which comprises the following steps:
Halide is dispersed in polar solvent, halide anions are obtained, the polar solvent is that can make the halide
Ionization forms the organic solvent of halide anions and halide cation；
The quantum dot that oil-soluble ligand is contained on surface is provided, by the quantum dot and the halide anions mixed processing, institute
Exchange reaction occurs for the ligand for stating halide anions and the quantum dot surface, and the amount of halide anions modification is prepared
Sub- point；
The quantum dot that the halide anions modification is deposited on substrate, prepares prefabricated quantum dot solid film；
The prefabricated quantum dot solid film is mixed with halide ion, makes the prefabricated quantum dot solid film and halide ion knot
It closes, obtains quantum dot solid film.
6. the preparation method of quantum dot solid film as claimed in claim 5, which is characterized in that wherein, the halide is MXm,
The halide anions are [MXm+n]n-, wherein M is selected from one of Pb, Cd, Zn, In, Fe, Fe, Sb, and X is selected from Cl, Br, I
One of, m is the valence number of M, and n is the valence mumber of the halide anions, wherein m is 2 or 3, and when m is 2, n is
1；When m is 3, n is 1 or 2.
7. the preparation method of quantum dot solid film as claimed in claim 5, which is characterized in that alms giver's number of the polar solvent
For 10-50.
8. the preparation method of quantum dot solid film as claimed in claim 7, which is characterized in that the organic solvent is selected from methyl
At least one of formamide, propylene carbonate, dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethyl alcohol, propyl alcohol.
9. such as the preparation method of the described in any item quantum dot solid films of claim 5-8, which is characterized in that by the quantum dot
In the step of the halide anions mixed processing, according to the quality mole of the quantum dot and the halide anions
Than the ratio mixed processing for 100mg:(0.2~1mmol).
10. such as the preparation method of the described in any item quantum dot solid films of claim 5-8, which is characterized in that will be described prefabricated
In the step of quantum dot solid film is mixed with halide ion, comprising:
Solution containing halide ion is provided, the prefabricated quantum dot solid film is immersed in the molten of the solution containing halide ion
In liquid.
11. a kind of battery device, which is characterized in that including light absorbing layer, and the light absorbing layer is any one of claim 1-4
The quantum dot solid film.
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| CN106566529A (en) * | 2016-11-10 | 2017-04-19 | Tcl集团股份有限公司 | Passivated quantum dot and preparation method thereof |
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| CN106566529A (en) * | 2016-11-10 | 2017-04-19 | Tcl集团股份有限公司 | Passivated quantum dot and preparation method thereof |
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| CN114907846A (en) * | 2021-02-10 | 2022-08-16 | 华中科技大学 | Quantum dot material, preparation method and application |
| CN114907846B (en) * | 2021-02-10 | 2023-08-01 | 华中科技大学 | Quantum dot material, preparation method and application |
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