CN110305656A - A kind of nanoparticle and preparation method thereof, quantum dot optoelectronic devices - Google Patents
A kind of nanoparticle and preparation method thereof, quantum dot optoelectronic devices Download PDFInfo
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- CN110305656A CN110305656A CN201910439151.XA CN201910439151A CN110305656A CN 110305656 A CN110305656 A CN 110305656A CN 201910439151 A CN201910439151 A CN 201910439151A CN 110305656 A CN110305656 A CN 110305656A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 231
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000005693 optoelectronics Effects 0.000 title claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 155
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 59
- -1 siloxanes Chemical class 0.000 claims description 58
- 150000003839 salts Chemical class 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 238000000746 purification Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 150000001768 cations Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 230000033228 biological regulation Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000005358 mercaptoalkyl group Chemical group 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 238000006862 quantum yield reaction Methods 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 8
- 238000012869 ethanol precipitation Methods 0.000 description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 6
- 239000004246 zinc acetate Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229940031098 ethanolamine Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/04—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
Abstract
The invention discloses a kind of nanoparticles and preparation method thereof, quantum dot optoelectronic devices.Wherein nanoparticle includes quantum dot and the first ligand and Ligands for being connected to quantum dot surface, and the first ligand is connected to the polar surfaces of quantum dot by chemical bond, and Ligands are adsorbed in the apolar surfaces of quantum dot, and Ligands form cross-linked structure.Nanoparticle stability of the invention is good, and preparation cost is relatively low.
Description
Technical field
The present invention relates to the surface treatments of quanta point material more particularly to a kind of nanoparticle and preparation method thereof, quantum
Point photoelectric device.
Background technique
Quantum dot is a kind of semiconductor nano crystal grain, also referred to as semiconductor nano.Quantum dot possesses unique light performance,
Quanta point material has very extensive application prospect in light-emitting electronic devices, photosensitive sensor, biology, medical domain.
Quantum dot is due to small-sized, large specific surface area, and there is the unoccupied orbital not being occupied by an electron much on surface, swashs electricity
Son can be captured by these unoccupied orbitals, these electronics would not move back and issue photon, to cause fluorescent quenching.In order to obtain height
The quanta point material of stability, it is necessary to quantum dot surface is modified, it is special by modification Effective Regulation quantum dot surface
Property.To quanta point material surface modification, there are two main classes at present: one kind is the shell thicker in quantum dot outer cladding, passes through increase
Surface defect achievees the purpose that improve quantum dot stability at a distance from the centre of luminescence, but this mode is only to photic quantum dot
Effectively, and its higher cost；Another kind of is using ligand passive quantum dot surface, to improve the stability of quantum dot, ligand
General structure be one end have the functional group containing lone pair electrons, as carboxyl, sulfydryl and amino etc., the other end be used to determine
The dissolubility and dispersibility of quantum dot.
Studies have shown that the surface of quantum dot is divided into polar surfaces and apolar surfaces, the ligand of polar surfaces is electrically charged
Ligand, and the ligand of apolar surfaces is not charged, and the ligand of apolar surfaces generally includes carboxylate, organic amine, organic phosphine
Deng, therefore the interaction of the ligand and non-polar plane of apolar surfaces is weaker, ligand is easy to fall off, to influence quantum dot
Stability.It is that various quantum dots are universal since the surface of any quantum dot all has the problem of non-polar plane, ligand falls off
There are problems that and urgent need to resolve.
In the synthesis process of quantum dot, the metal salt in reaction system also has certain suction in quantum dot apolar surfaces
It is attached, but metal salt ligands have certain chemical activity, there is the possibility being reduced, cause such ligand also unstable.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of nanoparticles that surface ligand is stable
And preparation method thereof
According to an aspect of the present invention, a kind of nanoparticle, including quantum dot are provided, above-mentioned quantum dot has polarity table
Face and apolar surfaces, which is characterized in that above-mentioned nanoparticle further includes above-mentioned quantum dot is connected to by chemical bond above-mentioned
First ligand groups of polar surfaces and be adsorbed in above-mentioned quantum dot above-mentioned apolar surfaces Ligands, above-mentioned second
Ligand includes multiple absorption ends and multiple crosslinked groups, and above-mentioned absorption end is adsorbed in the above-mentioned nonpolar table of above-mentioned quantum dot
Face, in which:
Each above-mentioned absorption end and at least two above-mentioned crosslinked groups by chemistry key connection, each above-mentioned crosslinked group with extremely
Few two above-mentioned absorption ends pass through chemistry key connection；
Alternatively, each above-mentioned absorption end and an above-mentioned crosslinked group be by chemistry key connection, each above-mentioned crosslinked group with
At least other two above-mentioned crosslinked group passes through chemistry key connection.
Above-mentioned absorption end is metal cation, the structure of above-mentioned crosslinked group in one of the embodiments, are as follows:
Wherein R1、R2、R3Respectively indicate alkyl or the alkyl with substituent group, above-mentioned metal cation and at least two
The oxygen atom of above-mentioned crosslinked group passes through chemistry key connection.
Above-mentioned R in one of the embodiments,1, above-mentioned R2, above-mentioned R3At least one of be carbon chain lengths 8~18 length
Alkyl group.
Above-mentioned R in one of the embodiments,1, above-mentioned R2, above-mentioned R3The respectively short-chain alkyl of carbon chain lengths 1~4.
Above-mentioned absorption end is sulfydryl, above-mentioned Ligands in one of the embodiments, are as follows:
Wherein n >=2, R5、R6、R7、R8Respectively indicate alkyl or the alkyl with substituent group.
Above-mentioned first ligand groups are R in one of the embodiments,4-S-, wherein R4For with functional group or without official
The alkyl that can be rolled into a ball, the cation of the above-mentioned polar surfaces of the sulphion and above-mentioned quantum dot of above-mentioned first ligand groups pass through chemistry
Key connection, it is preferable that above-mentioned R4Including 4~12 backbone carbon atoms.
According to another aspect of the present invention, a kind of preparation method of nanoparticle is provided, comprising the following steps:
S1 disperses the quantum dot with polar surfaces and apolar surfaces in the first solvent, be added the first ligand into
Row reaction, so that above-mentioned first ligand groups are connected to the above-mentioned polar surfaces of above-mentioned quantum dot, above-mentioned first ligand is to silicon
Oxygen alkane inertia；
S2 purifies above-mentioned quantum dot from the system after above-mentioned steps S1 reaction, then by the above-mentioned quantum dot of purification point
It dissipates and obtains quantum dot solution in the second solvent；
Metal salt is added in S3, Xiang Shangshu quantum dot solution to be reacted, so that above-mentioned metal salt is adsorbed in above-mentioned amount
The above-mentioned apolar surfaces of son point, then add siloxanes, regulation system to alkalinity so that the hydrolysis of above-mentioned siloxanes and with
Above-mentioned reacting metal salt, so that the above-mentioned apolar surfaces in above-mentioned quantum dot form Ligands, the metal of above-mentioned metal salt
The valence state of cation is+divalent or+divalent more than, above-mentioned siloxanes has at least two alkoxies；
Alternatively, sulfydryl siloxanes is added into above-mentioned quantum dot solution, above-mentioned sulfydryl siloxanes has at least two alkoxies
And an at least mercaptoalkyl, regulation system to alkalinity, so that above-mentioned sulfydryl siloxanes hydrolyzes and is cross-linked with each other to form second
Ligand, above-mentioned Ligands are adsorbed on the above-mentioned apolar surfaces of above-mentioned quantum dot by sulfydryl.
In one of the embodiments, in above-mentioned steps S1, above-mentioned first ligand is mercaptan.
The additional amount of above-mentioned first ligand is no less than the 30% of above-mentioned quantum dot gross mass in one of the embodiments,.
Above-mentioned metal salt is metal salt of organic carboxylic acid or inorganic acid metal salts in one of the embodiments, it is preferable that on
State short chain carboxy acid's metal salt that metal salt is carbon chain lengths 1~8.
The structure of above-mentioned siloxanes is that 2 alkoxies and 2 alkyl are connected on Si atom in one of the embodiments,
Or the structure of above-mentioned siloxanes is that 3 alkoxies and 1 alkyl are connected on Si atom；Preferably, in above-mentioned siloxane structure
An at least abovementioned alkyl be carbon chain lengths 8~18 chain alkyl or the abovementioned alkyl in above-mentioned siloxane structure be
The short-chain alkyl of carbon chain lengths 1~4.
In one of the embodiments, in above-mentioned steps S2,2 times or 2 times or more purifications are carried out to above-mentioned quantum dot, with
Removal is adsorbed in the substance of the above-mentioned apolar surfaces of above-mentioned quantum dot, and it is molten then to disperse second for the above-mentioned quantum dot of purification
Quantum dot solution is obtained in agent.
In one of the embodiments, above-mentioned steps S1 the following steps are included:
S11 provides the quantum dot with polar surfaces and apolar surfaces, the above-mentioned polar surfaces connection of above-mentioned quantum dot
There is third ligand, the above-mentioned apolar surfaces of above-mentioned quantum dot are adsorbed with the 4th ligand；
S12 cleans and purifies above-mentioned quantum dot, and to remove above-mentioned 4th ligand, the above-mentioned quantum dot after purification is dispersed
In the first solvent, the first ligand is then added, above-mentioned first ligand and above-mentioned third ligand carry out ligand exchange reaction, thus
Above-mentioned first ligand groups are connected to the above-mentioned polar surfaces of above-mentioned quantum dot；
Alternatively, S12, disperses above-mentioned quantum dot in the first solvent, be then added the first ligand, above-mentioned first ligand with
Above-mentioned third ligand carries out ligand exchange reaction, so that above-mentioned first ligand groups are connected to the polar surfaces of above-mentioned quantum dot.
In one of the embodiments, in above-mentioned steps S12 or above-mentioned steps S2, the specific side of above-mentioned quantum dot is purified
Method are as follows: above-mentioned quantum dot is mixed with tetramethylethylenediamine and non-coordinating solvent, after 60~100 DEG C of reaction a period of times,
Precipitating reagent is added and purifies above-mentioned quantum dot.
According to another aspect of the present invention, a kind of quantum dot optoelectronic devices are provided, including the above-mentioned nanoparticle of the present invention
Son.
Compared with prior art, the beneficial effects of the present invention are: the present invention is crosslinked the ligand of quantum dot apolar surfaces
A cross-linked structure is formed, so that the ligand of quantum dot apolar surfaces is not easily to fall off, to improve the stability of quantum dot；This
Invention is using the ligand of silicone cross-linked quantum dot apolar surfaces, and siloxanes is easy to get and cost is relatively low, therefore of the invention receives
The advantage of lower cost of rice corpuscles.
Detailed description of the invention
Figure 1A is the schematic diagram of one embodiment of nanoparticle of the present invention；
Figure 1B is the schematic diagram of another embodiment of nanoparticle of the present invention；
Fig. 2A shows the schematic diagram of the apolar surfaces adsorbing metal salt (zinc polycarboxylate) of quantum dot；
Fig. 2 B shows the schematic diagram of one embodiment of the Ligands of the apolar surfaces of quantum dot, wherein metal sun
Apolar surfaces of the ionic adsorption in quantum dot；
Fig. 2 C shows the schematic diagram of another embodiment of the Ligands of the apolar surfaces of quantum dot, wherein sulfydryl
It is adsorbed on the apolar surfaces of quantum dot；
Fig. 3 is the flow diagram of one embodiment of the preparation method of nanoparticle of the invention.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
It should be noted that the term " first ", " second " etc. in the description and claims of this application are to be used for
Similar object is distinguished, without being used to describe a particular order or precedence order.It should be understood that the data used in this way are suitable
It can be interchanged in the case of, so as to embodiments herein described herein.In addition, term " includes " and " having " and they
Any deformation, it is intended that cover it is non-exclusive include, for example, containing the process, method of a series of steps or units, being
System, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include be not clearly listed or
For the intrinsic other step or units of these process, methods, product or equipment.
The present invention provides a kind of nanoparticle comprising quantum dot QD, quantum dot QD have polar surfaces P and nonpolar table
Face N.Nanoparticle further includes the first ligand groups X and the absorption that the polar surfaces P of quantum dot QD is connected to by chemical bond
In the Ligands of the apolar surfaces N of quantum dot QD.Ligands include multiple absorption end F and multiple crosslinked group G, are inhaled
Attached end F is adsorbed in the apolar surfaces N of quantum dot QD, in which:
Each absorption end F and at least two crosslinked group G passes through chemistry key connection, each crosslinked group G and at least two absorption
Hold F by chemistry key connection, as shown in Figure 1A；
Alternatively, an each absorption end F and crosslinked group G passes through chemistry key connection, each crosslinked group G and at least other two
Crosslinked group G is by chemistry key connection, as shown in Figure 1B.
It will be appreciated by those skilled in the art that yes, Figure 1A, Figure 1B are merely for convenience to understand nanoparticle of the invention
The schematical attached drawing provided, quantum dot QD, polar surfaces P, apolar surfaces N, the first X ligand, absorption end F, crosslinking in figure
Shape, size, quantity of group G etc. are signal, do not imply that each material demand has shape shown in figure, size or number
Amount etc.；In addition, the ligand of other surfaces is not shown to put it more simply, only illustrating the ligand of the part of the surface of quantum dot QD in figure.
In nanoparticle provided by the invention, the polar surfaces of the first ligand groups and quantum dot are keyed by chemistry,
Its connective stability is good, not easily to fall off；The connection type of Ligands and quantum dot surface is absorption, active force and chemical bond
It compared to weaker, but since Ligands form cross-linked structure, is integrally not easy to fall off from quantum dot surface, therefore of the invention receives
Rice corpuscles stability is good.In addition, Ligands can be made by siloxanes, siloxanes is easy to get and cost is relatively low, therefore the present invention receives
The cost of rice corpuscles is unlikely to too high.
In some embodiments, as shown in Figure 1A, absorption end F is metal cation, the structure of crosslinked group G are as follows:
Wherein R1、R2、R3Respectively indicate alkyl or the alkyl with substituent group.Metal cation and at least two crosslinkings
The oxygen atom of group G is by chemistry key connection, with metal cation with the quantity of the crosslinked group G of chemistry key connection and metal sun
The valence state of ion is related, for example, when the valence state of metal cation is divalent, a metal cation and two crosslinked group G
Oxygen atom pass through chemistry key connection, when the valence state of metal cation is trivalent, a metal cation and three crosslinking groups
(in view of the influence of steric hindrance, a metal cation is substantially it is not possible that with same by chemistry key connection for the oxygen atom of group G
Two or more oxygen atoms of a crosslinked group G pass through chemistry key connection).
It will be appreciated by persons skilled in the art that above-mentioned crosslinked group G is remaining after losing multiple atoms or atomic group
Part namely the chemical bond of oxygen atom end be the chemical bond that is connect with the atom or atomic group lost of oxygen atom.In this hair
In bright some embodiments, the atom with the chemistry key connection of oxygen atom end is metal cation.
In some embodiments of Ligands, R1、R2、R3At least one of be carbon chain lengths 8~18 long alkane
Base, nanoparticle shows as oil-soluble at this time.
In other embodiments of Ligands, R1、R2、R3The respectively short-chain alkyl of carbon chain lengths 1~4, receives at this time
Rice corpuscles shows as alcohol-soluble.
In further embodiments, as shown in Figure 1B, absorption end F is sulfydryl, Ligands are as follows:
Wherein n >=2, R5、R6、R7、R8Respectively indicate alkyl or the alkyl with substituent group.
In some embodiments, the first ligand groups are R4-S-(R4"-" between sulphur atom indicates covalent bond), wherein
R4For with functional group or without the alkyl of functional group, the sun of the polar surfaces of the sulphur atom and quantum dot of the first ligand groups from
Son passes through chemistry key connection.In some cases, R4In include hydroxyl.Preferably, R4Including 4~12 backbone carbon atoms, R4It can
To be to work as R without branch or with the straight chain of branch4When with branch, aforementioned backbone carbon atoms include constituting main chain and branch
Backbone carbon atoms.
The present invention also provides a kind of preparation methods of nanoparticle, comprising the following steps:
S1 disperses the quantum dot with polar surfaces and apolar surfaces in the first solvent, be added the first ligand into
Row reaction, so that the first ligand groups are connected to the polar surfaces of quantum dot, the first ligand is to siloxanes inertia；
S2 purifies quantum dot from the system after step S1 reaction, then disperses the second solvent for the quantum dot of purification
In obtain quantum dot solution；
S3 is added metal salt into quantum dot solution and is reacted, so that metal salt is adsorbed in the nonpolarity of quantum dot
Surface, then adds siloxanes, regulation system to alkalinity so that siloxanes hydrolysis and and reacting metal salt, thus measuring
The apolar surfaces of son point form Ligands, the valence state of the metal cation of metal salt is+divalent or+divalent more than, siloxanes
With at least two alkoxies；
Alternatively, sulfydryl siloxanes is added into quantum dot solution, sulfydryl siloxanes is at least two alkoxies and at least
One mercaptoalkyl, regulation system to alkalinity, so that sulfydryl siloxanes hydrolyzes and is cross-linked with each other to form Ligands, Ligands
Sulfydryl be adsorbed on the apolar surfaces of quantum dot.
It is mainly to protect the polar surfaces of quantum dot in the purpose that polar surfaces connect the first ligand in step S1, due to
First ligand shows inertia to siloxanes, therefore step S3 is added siloxanes or when sulfydryl siloxanes prepares Ligands, silicon
Oxygen alkane will not influence the first ligand in the connection of quantum dot surface.The purpose of step S2 is to remove the apolar surfaces of quantum dot
The substance of upper absorption, to guarantee in subsequent step, metal salt or sulfydryl can smoothly be adsorbed on the apolar surfaces of quantum dot.
In one embodiment, the purpose of step S3 is the apolar surfaces formation in quantum dot to cross-linked surface, gold
Belong to the metal cation adsorption in salt in quantum dot surface, the other end of metal salt extends outwardly, after siloxanes is added, by system
It is adjusted to alkalinity, crosslinked group can be formed after siloxanes hydrolysis, each crosslinked group has at least two oxonium ions, each metal
The oxonium ion of cation and at least two crosslinked groups is keyed by chemistry, to form the second of crosslinking in apolar surfaces
Ligand.The siloxanes that the embodiment uses is easy to get and cost is relatively low, and practicability is good, the nanoparticle stability being prepared
Good, quantum yield is high.By taking metal salt is zinc polycarboxylate, siloxanes is siloxanes of the tool there are two alkoxy as an example, Fig. 2A is shown
Metal salt is adsorbed on the state of quantum dot apolar surfaces, and Fig. 2 B shows that the Ligands of crosslinking are adsorbed on quantum dot nonpolarity
The schematic diagram of the one embodiment on surface.
In another embodiment, the purpose of step S3 is so that it is adsorbed on quantum in the sulfydryl using sulfydryl siloxanes
The apolar surfaces of point, then make sulfydryl silicone cross-linked, to form the Ligands of crosslinking in apolar surfaces.The implementation
The preparation method of mode is simple, and the nanoparticle stability being prepared is good, and quantum yield is high.Fig. 2 C shows the second of crosslinking
Ligand is adsorbed on the schematic diagram of another embodiment of quantum dot apolar surfaces.
In some embodiments, the first ligand is mercaptan, and the effect of mercaptan and polar surface is very strong, will not be siliconized.
In some embodiments, in step S1, the additional amount of the first ligand is no less than the 30% of quantum dot gross mass, the amount
Son point gross mass refers to the gross mass of the initial quantum dot of step S1 (including following initial ligands).
In some embodiments, in step S3, metal salt is metal salt of organic carboxylic acid or inorganic acid metal salts.Preferably,
Metal salt is short chain carboxy acid's metal salt of carbon chain lengths 1~8, and the steric hindrance of short chain carboxy acid's metal salt is small, with subsequent addition
The reactivity of siloxanes can be higher, advantageously reduces the probability that self-polymeric reaction occurs for siloxanes.
In some embodiments, the structure of siloxanes is that 2 alkoxies and 2 alkyl or silicon oxygen are connected on Si atom
The structure of alkane is that 3 alkoxies and 1 alkyl are connected on Si atom.It should be noted that above-mentioned siloxanes can be selected from one kind
Siloxanes with above-mentioned structure feature can also be selected from the siloxanes of a variety of structure features having the same, " identical knot
Structure feature " refers to that each selected siloxanes has the similar substituent group of identical quantity.In some cases, siloxane structure
In an at least alkyl be carbon chain lengths 8~18 chain alkyl, nanoparticle obtained is oil-soluble at this time.In other feelings
Under condition, the alkyl in siloxane structure is the short-chain alkyl of carbon chain lengths 1~4, and nanoparticle obtained is alcohol-soluble at this time.
Alkoxy in siloxane structure includes 1~3 carbon.
In further embodiments, the structure of sulfydryl siloxanes is that 2 alkoxies, 1 alkyl and one are connected on Si atom
The structure of a mercaptoalkyl or sulfydryl siloxanes is that 3 alkoxies and 1 mercaptoalkyl are connected on Si atom.Wherein, sulfydryl
The structure of alkyl are as follows:-R-SH.
It is noted that being added before the first ligand, the surface of quantum dot, which is generally connected with, initially matches in step S1
Body, initial ligand are usually on the polar surfaces and apolar surfaces for being just connected to quantum dot when synthesizing quantum dot, even
The siloxanes that connecing the initial ligand in polar surfaces may be added in subsequent step aoxidizes, so as to cause quantum point-polarity table
Face is destroyed, and the initial ligand for being connected to apolar surfaces may will affect the absorption of subsequent metal salt, based on the above reasons, amount
The initial ligand needs on son point surface are replaced or remove.In step sl, the first ligand of addition can be anti-by ligand exchange
The initial ligand of quantum dot polar surfaces should be replaced, and quantum dot is cleaned, is purified, it is non-quantum dot can be got rid of
The removal of the initial ligand namely initial ligand of polar surfaces mainly passes through ligand exchange and cleaning purification is realized.
In one embodiment, step S1 the following steps are included:
S11, provides the quantum dot with polar surfaces and apolar surfaces, and the polar surfaces of quantum dot are connected with third and match
Body, the apolar surfaces of quantum dot are adsorbed with the 4th ligand；
S12a cleans and purifies quantum dot, and to remove the 4th ligand, the quantum dot after purification is dispersed in the first solvent
In, the first ligand is then added, the first ligand and third ligand carry out ligand exchange reaction, so that the first ligand groups are connected to
The polar surfaces of quantum dot.
In the embodiment, after step S12a and step S2, the initial ligand of quantum dot surface is substantially removed.
In a specific embodiment of step S12a, the step of cleaning and purify quantum dot are as follows: by quantum dot and tetramethyl
Base ethylenediamine and non-coordinating solvent mixing are added precipitating reagent and purify quantum dot after 60~100 DEG C of reaction a period of times.
In a specific embodiment of step S2, the method for quantum dot is purified from the system after step S12a reaction
Are as follows: precipitating reagent is added and purifies quantum dot 2 times.
In another embodiment, step S1 the following steps are included:
S11, provides the quantum dot with polar surfaces and apolar surfaces, and the polar surfaces of quantum dot are connected with third and match
Body, the apolar surfaces of quantum dot are adsorbed with the 4th ligand；
S12b, above-mentioned quantum dot is dispersed in the first solvent, and the first ligand, the first ligand and third ligand is then added
Ligand exchange reaction is carried out, so that the first ligand groups are connected to the polar surfaces of quantum dot.
In the embodiment, after step S12b and step S2, the initial ligand of quantum dot surface is substantially removed.
In a specific embodiment of step S2, the method for quantum dot is purified from the system after step S12b reaction
Are as follows: quantum dot is mixed with tetramethylethylenediamine and non-coordinating solvent, after 60~100 DEG C of reaction a period of times, it is heavy to be added
Shallow lake agent purifies quantum dot.
In some embodiments, third ligand is carboxylate radical, and the 4th ligand is carboxylate, organic amine, one in organic phosphine
Kind is a variety of.
In some embodiments, in step S2, the step of purifying quantum dot are as follows: by quantum dot and tetramethylethylenediamine and
Non-coordinating solvent mixing is added precipitating reagent and purifies quantum dot after 60~100 DEG C of reaction a period of times.
In some embodiments, in step S2,2 times or 2 times or more purifications are carried out, to quantum dot to remove the amount of being adsorbed in
The substance of son point apolar surfaces.
Fig. 3 is the schematic diagram of one embodiment of nanoparticle preparation method of the invention, and those skilled in the art can be with
Understand yes, Fig. 3 schematical attached drawing merely for convenience for understanding nanoparticle of the invention and providing, quantum dot QD in figure,
First ligand, Ligands, third ligand, the 4th ligand, the shape of metal salt, size, quantity etc. are signal, are not implied that
Each material demand has shape shown in figure, size or quantity etc.；In addition, to put it more simply, only illustrating quantum dot QD in figure
Part of the surface ligand, the ligand of other surfaces is not shown.In Fig. 3, the initial ligand on the surface quantum dot (QD) is matched for third
To remove the 4th ligand for being adsorbed on apolar surfaces, then body and the 4th ligand clean quantum dot and are purified first
It adds the first ligand and carries out ligand exchange, the first ligand is connected to the polar surfaces of quantum dot instead of third ligand, to quantum
Point purification after (not shown), then plus metal salt, so that metal salt is adsorbed on the apolar surfaces of quantum dot, then add silicon
Oxygen alkane reaction, so that the apolar surfaces in quantum dot form the Ligands being crosslinked mutually.
The present invention also provides a kind of quantum dot optoelectronic devices, including present invention nanoparticle above-mentioned, or by the present invention
The nanoparticle that preceding method is prepared.Quantum dot optoelectronic devices can be but not limited to electroluminescent diode, photic hair
Optical diode, display, solar battery etc..It is worth noting that, when quantum dot optoelectronic devices are electroluminescent diode, this
Nanoparticle above-mentioned or the nanoparticle being prepared by preceding method of the present invention are invented as electroluminescent diode
When emitting layer material, aforementioned nanoparticle is not in the preparation to influence the photoelectric properties of quantum dot as implementation standard.
[embodiment 1]
A kind of nanoparticle is provided, is prepared by following steps:
(1) 0.5g green quantum dot, 0.5g tetramethylethylenediamine, 0.1g butylamine is taken to be added in 5mL toluene, at 100 DEG C
15min is heated, the centrifugation of 10mL ethanol precipitation is then added, adds the centrifugation of 10mL ethanol precipitation after being redissolved in 5mL toluene
Obtain the quantum dot of pre- purification；
(2) quantum dot purified in advance is dispersed in the dimethyl sulfoxide that 10mL contains 0.5g ethanol amine to obtain quantum dot molten
Liquid takes the different spicy thioalcohol of 0.3g, adjusts pH to alkalinity with tetramethylammonium hydroxide, is added dropwise in aforementioned quantum dot solution, shakes molten
30min is reacted after solution, then purifies quantum dot twice using ethyl acetate as precipitating reagent；
(3) quantum dot of purification is dissolved in the dimethyl sulfoxide of 10mL, 0.3g zinc acetate is added, is reacted at 120 DEG C
20min is subsequently added into 10mL octane, the methanol solution of 6mL hexadecyl and 6mL tetramethylammonium hydroxide
(mass fraction 25%), the Ligands that stirring 1h is crosslinked mutually in quantum dot surface at 70 DEG C, is precipitated with ethyl alcohol
Agent purifies quantum dot 2 times, is then dissolved in octane and saves.
[embodiment 2]
A kind of nanoparticle is provided, is prepared by following steps:
(1) 0.5g green quantum dot, 0.5g tetramethylethylenediamine, 0.1g butylamine is taken to be added in 5mL toluene, at 100 DEG C
15min is heated, the centrifugation of 10mL ethanol precipitation is then added, adds the centrifugation of 10mL ethanol precipitation after being redissolved in 5mL toluene
Obtain the quantum dot of pre- purification；
(2) quantum dot purified in advance is dispersed in the dimethyl sulfoxide that 10mL contains 0.5g ethanol amine to obtain quantum dot molten
Liquid takes 0.3g sulfydryls hexanol, adjusts pH to alkalinity with tetramethylammonium hydroxide, is added dropwise in aforementioned quantum dot solution, shakes molten
30min is reacted after solution, then purifies quantum dot twice using ethyl acetate as precipitating reagent；
(3) quantum dot of purification is dissolved in the dimethyl sulfoxide of 10mL, 0.3g zinc acetate is added, is reacted at 120 DEG C
20min, being subsequently added into the methanol solution of 3mL ethyl triethoxysilane and 6mL tetramethylammonium hydroxide, (mass fraction is
25%), the Ligands that stirring 1h is crosslinked mutually in quantum dot surface at 70 DEG C, make precipitating reagent purification amount with ethyl acetate
Son point 2 times, is then dissolved in ethyl alcohol and saves.
[embodiment 3]
A kind of nanoparticle is provided, is prepared by following steps:
(1) 0.5g green quantum dot, 0.5g tetramethylethylenediamine, 0.1g butylamine is taken to be added in 5mL toluene, at 100 DEG C
15min is heated, the centrifugation of 10mL ethanol precipitation is then added, adds the centrifugation of 10mL ethanol precipitation after being redissolved in 5mL toluene
Obtain the quantum dot of pre- purification；
(2) quantum dot purified in advance is dispersed in the dimethyl sulfoxide that 10mL contains 0.5g ethanol amine to obtain quantum dot molten
Liquid takes 0.3g sulfydryls hexanol, adjusts pH to alkalinity with tetramethylammonium hydroxide, is added dropwise in aforementioned quantum dot solution, shakes molten
30min is reacted after solution, then purifies quantum dot twice using ethyl acetate as precipitating reagent
(3) quantum dot of purification is dissolved in the dimethyl sulfoxide of 10mL, 0.3g zinc acetate is added, is reacted at 120 DEG C
20min, being subsequently added into the methanol solution of 3mL dimethyldimethoxysil,ne and 6mL tetramethylammonium hydroxide, (mass fraction is
25%), the Ligands that stirring 1h is crosslinked mutually in quantum dot surface at 70 DEG C, make precipitating reagent purification amount with ethyl acetate
Son point 2 times, is then dissolved in ethyl alcohol and saves.
[embodiment 4]
A kind of nanoparticle is provided, is prepared by following steps:
(1) 0.5g green quantum dot is dispersed in the octane of 10mL and obtains quantum dot solution；
(2) it takes 0.3g sulfydryls hexanol to be added in 10ml dimethyl sulfoxide, adjusts solution to alkalinity with tetramethylammonium hydroxide,
10min is reacted after concussion dissolution, obtains mixed solution；
(3) 30min is reacted after the quantum dot solution of step (1) and the mixed solution of step (2) being mixed concussion, takes diformazan
Base sulfoxide is added to 20ml ethyl acetate and obtains quantum dot precipitating；
(4) above-mentioned quantum dot precipitating is dispersed in 10ml dimethyl sulfoxide, 0.5g tetramethylethylenediamine, 0.5g second is added
Hydramine heats 15min at 100 DEG C, and the precipitating centrifugation of 20mL ethyl acetate is then added, obtains the quantum dot of pre- purification；
(5) quantum dot purified in advance is dissolved in the dimethyl sulfoxide of 10mL, 0.3g zinc acetate is added, it is anti-at 120 DEG C
20min is answered, the methanol solution of 3mL dimethyldimethoxysil,ne and 6mL tetramethylammonium hydroxide is then added, and (mass fraction is
25%), the Ligands that stirring 1h is crosslinked mutually in quantum dot surface at 70 DEG C, make precipitating reagent purification amount with ethyl acetate
Son point 2 times, is then dissolved in ethyl alcohol and saves.
[embodiment 5]
The difference from example 2 is that: zinc acetate is replaced using cadmium acetate in step (3).
[comparative example 1]
0.5g green quantum dot preparation quantum dot solution (identical as the raw material green quantum dot in embodiment 1) is taken, is carried out
Stability test.
[comparative example 2]
A kind of nanoparticle is provided, is prepared by following steps:
(1) 0.5g green quantum dot, 0.5g tetramethylethylenediamine, 0.1g butylamine is taken to be added in 5mL toluene, at 100 DEG C
15min is heated, the centrifugation of 10mL ethanol precipitation is then added, adds the centrifugation of 10mL ethanol precipitation after being redissolved in 5mL toluene
Obtain the quantum dot of pre- purification；
(2) quantum dot purified in advance is dispersed in the dimethyl sulfoxide that 10mL contains 0.5g ethanol amine to obtain quantum dot molten
Liquid takes 0.3g sulfydryls hexanol, adjusts pH to alkalinity with tetramethylammonium hydroxide, is added dropwise in aforementioned quantum dot solution, shakes molten
30min is reacted after solution, is then purified quantum dot 2 times using ethyl acetate as precipitating reagent；
(3) quantum dot of purification is dissolved in the dimethyl sulfoxide of 10mL, 0.3g zinc acetate is added, is reacted at 120 DEG C
20min makees precipitating reagent with ethyl acetate and purifies quantum dot 2 times, is then dissolved in ethyl alcohol and saves.
The quantum dot of the various embodiments described above and comparative example is spin-coated on glass (film thickness 80nm), under condition of nitrogen gas respectively
It anneals 1 hour at 150 DEG C, 200 DEG C, measurement annealing front and back film quantum yield (QY), test result is shown in Table 1.
Table 1
| Initial film QY | 150 DEG C of annealing | 200 DEG C of annealing | |
| Embodiment 1 | 78% | 74% | 67% |
| Embodiment 2 | 83% | 80% | 75% |
| Embodiment 3 | 82% | 77% | 71% |
| Embodiment 4 | 81% | 76% | 71% |
| Embodiment 5 | 85% | 82% | 78% |
| Comparative example 1 | 81% | 74% | 64% |
| Comparative example 2 | 77% | 68% | 52% |
From the data of table 1 it can be found that after the 1h that anneals at 150 DEG C of each quantum dot of embodiment 1-5, the decline of quantum yield
It is 3%~5%, and after the 1h that anneals at 150 DEG C of the quantum dot of comparative example, the decline of quantum yield reaches 7% or more；Embodiment 1-
It is annealed after 1h at 200 DEG C of each quantum dot of 5, quantum yield falls to 7%~11%, and at 200 DEG C of the quantum dot of comparative example
It anneals after 1h, the decline of quantum yield reaches 17% or more.As it can be seen that being improved in the Ligands that quantum dot surface obtains crosslinking
The stability of quantum dot.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (15)
1. a kind of nanoparticle, including quantum dot, the quantum dot has polar surfaces and apolar surfaces, which is characterized in that
The nanoparticle further include be connected to by chemical bond the polar surfaces of the quantum dot the first ligand groups and
It is adsorbed in the Ligands of the apolar surfaces of the quantum dot, the Ligands include multiple absorption ends and multiple
Crosslinked group, the absorption end are adsorbed in the apolar surfaces of the quantum dot, in which:
Each absorption end and at least two crosslinked groups pass through chemistry key connection, each crosslinked group and at least two
The absorption end passes through chemistry key connection；
Alternatively, each absorption end and a crosslinked group be by chemistry key connection, each crosslinked group at least
Other two crosslinked group passes through chemistry key connection.
2. nanoparticle according to claim 1, which is characterized in that the absorption end is metal cation, the crosslinking
The structure of group are as follows:
Wherein R1、R2、R3Respectively indicate alkyl or the alkyl with substituent group, the metal cation at least described in two
The oxygen atom of crosslinked group passes through chemistry key connection.
3. nanoparticle according to claim 2, which is characterized in that the R1, the R2, the R3At least one of
For the chain alkyl of carbon chain lengths 8~18.
4. nanoparticle according to claim 2, which is characterized in that the R1, the R2, the R3Respectively carbon chain length
The short-chain alkyl of degree 1~4.
5. nanoparticle according to claim 1, which is characterized in that the absorption end is sulfydryl, the Ligands are as follows:
Wherein n >=2, R5、R6、R7、R8Respectively indicate alkyl or the alkyl with substituent group.
6. -5 any nanoparticle according to claim 1, which is characterized in that first ligand groups are R4-S-,
Middle R4For with functional group or without the alkyl of functional group, the sulphions of first ligand groups is described with the quantum dot
The cation of polar surfaces passes through chemistry key connection, it is preferable that the R4Including 4~12 backbone carbon atoms.
7. a kind of preparation method of nanoparticle, which comprises the following steps:
S1 disperses the quantum dot with polar surfaces and apolar surfaces in the first solvent, and the first ligand is added and carries out instead
It answers, so that the first ligand groups are connected to the polar surfaces of the quantum dot, first ligand is to siloxanes inertia；
S2 purifies the quantum dot from the system after step S1 reaction, then disperses the quantum dot of purification in
Quantum dot solution is obtained in second solvent；
Metal salt is added in S3, Xiang Suoshu quantum dot solution to be reacted, so that the metal salt is adsorbed in the quantum dot
The apolar surfaces, then add siloxanes, regulation system to alkalinity so that siloxanes hydrolysis and with it is described
Reacting metal salt, so that the apolar surfaces in the quantum dot form Ligands, the metal sun of the metal salt from
The valence state of son is+divalent or+divalent more than, the siloxanes has at least two alkoxies；
Alternatively, into the quantum dot solution be added sulfydryl siloxanes, the sulfydryl siloxanes have at least two alkoxies and
An at least mercaptoalkyl, regulation system to alkalinity, so that the sulfydryl siloxanes hydrolyzes and is cross-linked with each other to form Ligands,
The Ligands are adsorbed on the apolar surfaces of the quantum dot by sulfydryl.
8. the preparation method of nanoparticle according to claim 7, which is characterized in that in the step S1, described first
Ligand is mercaptan.
9. the preparation method of nanoparticle according to claim 7, which is characterized in that the additional amount of first ligand is not
Less than the 30% of the quantum dot gross mass.
10. the preparation method of nanoparticle according to claim 7, which is characterized in that the metal salt is organic carboxyl acid
Metal salt or inorganic acid metal salts, it is preferable that the metal salt is short chain carboxy acid's metal salt of carbon chain lengths 1~8.
11. the preparation method of nanoparticle according to claim 7, which is characterized in that the structure of the siloxanes is Si
The structure that 2 alkoxies and 2 alkyl or the siloxanes are connected on atom is that 3 alkoxies and 1 are connected on Si atom
Alkyl；Preferably, at least one alkyl in the siloxane structure is the chain alkyl of carbon chain lengths 8~18, Huo Zhesuo
State the short-chain alkyl that the alkyl in siloxane structure is carbon chain lengths 1~4.
12. the preparation method of nanoparticle according to claim 7, which is characterized in that in the step S2, to the amount
Son point progress 2 times or 2 times or more purifications, to remove the substance for the apolar surfaces for being adsorbed in the quantum dot, then
It disperses the quantum dot of purification in the second solvent and obtains quantum dot solution.
13. according to the preparation method of any nanoparticle of claim 7-12, which is characterized in that the step S1 includes
Following steps:
S11, provides the quantum dot with polar surfaces and apolar surfaces, and the polar surfaces of the quantum dot are connected with
The apolar surfaces of three ligands, the quantum dot are adsorbed with the 4th ligand；
S12 cleans and purifies the quantum dot, and to remove the 4th ligand, the quantum dot after purification is dispersed in
In one solvent, the first ligand is then added, first ligand and the third ligand carry out ligand exchange reaction, thus first
Ligand groups are connected to the polar surfaces of the quantum dot；
Alternatively, S12, disperses the quantum dot in the first solvent, be then added the first ligand, first ligand with it is described
Third ligand carries out ligand exchange reaction, so that the first ligand groups are connected to the polar surfaces of the quantum dot.
14. the preparation method of nanoparticle according to claim 13, which is characterized in that the step S12 or described
In step S2, the quantum dot is purified method particularly includes: by the quantum dot and tetramethylethylenediamine and non-coordinating solvent
Mixing is added precipitating reagent and purifies the quantum dot after 60~100 DEG C of reaction a period of times.
15. a kind of quantum dot optoelectronic devices, which is characterized in that including any nanoparticle of claim 1-6, or packet
Include the nanoparticle as made from claim 7-14 any preparation method.
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