CN108641720A - A kind of quantum dot and its synthetic method - Google Patents
A kind of quantum dot and its synthetic method Download PDFInfo
- Publication number
- CN108641720A CN108641720A CN201810586981.0A CN201810586981A CN108641720A CN 108641720 A CN108641720 A CN 108641720A CN 201810586981 A CN201810586981 A CN 201810586981A CN 108641720 A CN108641720 A CN 108641720A
- Authority
- CN
- China
- Prior art keywords
- zinc
- quantum dot
- source
- sulphur
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
Abstract
The invention discloses a kind of quantum dot and its synthetic methods.The synthetic method includes：It synthesizes the first step of quantum dot core, coat the second step of an at least transition zone in the quantum dot core, and, the third step of shell is coated on the transition zone；Characterized by further comprising：In the first step, quantum dot core is performed etching with inorganic acid；And/or in the second step, an at least transition zone is performed etching with inorganic acid；And/or in third step, shell is performed etching with inorganic acid；Wherein, the halide anion contained by the inorganic acid, H+Halogen inorganic salt, the amine substance being respectively derived from the reaction system of first step, second step or third step.The present invention in the synthesis process performs etching quantum dot using inorganic acid, eliminates the anisotropy of quantum dot in the synthesis process, and method is more safely controllable, and the fluorescence quantum yield of quantum dot can be improved, and can also improve its optics, chemically and thermally stability.
Description
Technical field
The present invention relates to a kind of synthetic methods of quantum dot, more particularly to a kind of to use inorganic acid, are synthesized in quantum dot
The method performed etching to quantum dot in journey, belongs to technical field of nanometer material preparation.
Background technology
Quantum dot is to make its tool because it is with quantum local effect by a kind of molecular semiconductor crystal of several originals
There are good luminescent properties.Relative to other luminescent materials, it can be applicable to the necks such as display, illumination, biology, solar cell
Domain.
As the research to quantum dot gradually becomes deeply, how to improve the stability of quantum dot, luminous efficiency and subtract
Its small structure or defect become the Main way of industry research staff research.Although to the II-VI groups research such as CdSe, CdS when
Between for a long time, correlated performance also makes moderate progress, but also there is ample room for improvement for its overall application, and InP etc. is without cadmium amount
Son point then more needs to improve.
It is improved for the performance of quantum dot, common gimmick has the methods of doping improvement, alloying, packing protective layer.
The quantum dot of luminosity purer (FWHM narrow, QY high), industry research staff much take two-step method in order to obtain
Or multistep processes is synthesized, but for multistep processes synthesis (high temperature notes core etc.), quantum dot core after purification can exist and water
The chance that oxygen combines so that core surface is aoxidized.But the quantum dot gone out with one pot process understands existing defects again on core, from
And causes anisotropy and occur bigger flaw in follow-up cladding process.
Document Spierings G A C M.Wet chemical etching of silicate glasses in
Hydrofluoric acid based solutions [J] .Journal ofMaterials Science, 1993,28 (23):
6261-6273 proposes some about the theory for using hf etching.Hua F J, Swihart M T, Ruckenstein
E.Efficient surfacegrafting of luminescent silicon quantum dots by
Photoinitiatedhydrosilylation [J] .Langmuir, 2005,21 (13):6054-6062 is it is also proposed that use nitric acid
It is tested as etching agent.But consider in the amplification for the quantum dot that compares production and experiment safety, these types etching is
There are prodigious risks.
Invention content
The main purpose of the present invention is to provide a kind of to carry out quantum dot in quantum dot building-up process using inorganic acid
The method of etching, with overcome the deficiencies in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of synthetic methods of quantum dot comprising：The first step of synthesis quantum dot core,
The second step of an at least transition zone is coated in the quantum dot core, and, the third step of shell is coated on the transition zone
Suddenly；The synthetic method further includes：In the first step, quantum dot core is performed etching with inorganic acid；And/or in second step
In rapid, an at least transition zone is performed etching with inorganic acid；And/or in third step, shell is carved with inorganic acid
Erosion；Wherein, the halide anion contained by the inorganic acid, H+It is respectively derived from first step, second step or third step
Halogen inorganic salt, amine substance in reaction system.
Further, the halogen inorganic salt is preferably halogen zinc salt.
Among certain preferred embodiments, the lithographic method includes：
Make the hybrid reaction system comprising indium source, zinc source, ligand solvent and non-coordinating solvent react in 150~200 DEG C 1~
30min obtains indium presoma and zinc precursor mixed liquor；
Phosphine source is added into the hybrid reaction system in 200~300 DEG C and forms quantum dot core InP and/or InZnP；
The quantum dot core is performed etching with inorganic acid.
Among certain preferred embodiments, the lithographic method includes：In the completion first step or to the amount
After the etching of son point core, selenium source, zinc source, the sulphur source for selectively adding or being added without and choosing are added into the hybrid reaction system
Selecting property is added or the inorganic salts that are added without, and reacts 1~60min in 150~300 DEG C, in coating ZnSe on the quantum dot core
Transition zone and/or ZnSeS layers, or it is performed etching while coating the ZnSe transition zones and/or ZnSeS layers.
Among certain preferred embodiments, the lithographic method includes：In the completion second step or to described
After ZnSe transition zones and/or ZnSeS layers of etching, sulphur source, zinc source are added into the hybrid reaction system and selectively adds
Or the inorganic salts being added without, and 1~60min is reacted in 280~320 DEG C, it is wrapped on the ZnSe transition zones and/or ZnSeS layers
It covers ZnS shells or it is performed etching while coating the ZnS shells.
The embodiment of the present invention additionally provides the quantum dot synthesized by preceding method, and the emission peak wave band of the quantum dot can
It adjusts, emission peak half-peak breadth is less than 45nm, and luminous efficiency is more than 70%.
Compared with tradition etches the method for quantum dot with acid-base class, the beneficial effects of the present invention are：
1) present invention performs etching quantum dot using inorganic salts, has not only participated in synthetic reaction in the synthesis process but also to quantum
Point complete etching, eliminate the anisotropy of quantum dot in the synthesis process, woth no need to by quantum dot it is synthetic after etch again,
Method is safer, and the amount of the acid formed in its etching can control, and can not only improve the fluorescent quantum production of quantum dot
Rate can also improve its optics, chemically and thermally stability, obtain the stable quantum-dot structure of growth；
2) H that the present invention is provided using halide anion with amine in reaction system+In conjunction with the corresponding inorganic acid of production
(HF, HCl, HBr) performs etching quantum dot core, transition zone or shell, can remove the defect of quantum dot, improves the hair of quantum dot
Light quality；
3) it can be to form ZnSe during the reaction that the present invention, which is preferentially it using the purpose of the halogen inorganic salt of Zn classes,
Or ZnSeS or ZnS provides Zn ions, later stage halide ion and H+It can be gone in quantum later purification after forming inorganic acid
It the gimmicks such as removes, or can also be vacuumized with high temperature to remove.
Description of the drawings
Fig. 1 for obtained quantum dot indium phosphide nucleocapsid in an of the invention typical embodiments launching light spectrogram.
Fig. 2 for obtained quantum dot in an of the invention typical embodiments TEM pictures.
Specific implementation mode
In view of deficiency in the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
A kind of synthetic method for quantum dot that the one side of the embodiment of the present invention provides comprising：Synthesize quantum dot core
First step, the quantum dot core coat an at least transition zone second step, and, the encasement on the transition zone
The third step of layer；The synthetic method further includes：In the first step, quantum dot core is performed etching with inorganic acid；With/
Or, in the second step, being performed etching to an at least transition zone with inorganic acid；And/or in third step, with inorganic acid pair
Shell performs etching；Wherein, the halide anion contained by the inorganic acid, H+Be respectively derived from first step, second step or
Halogen inorganic salt, amine substance in the reaction system of third step.
Among certain preferred embodiments, the lithographic method includes：It is initially formed the quantum dot core, then using inorganic
Salt performs etching the quantum dot core.
Among certain preferred embodiments, the lithographic method includes：In the process that the transition zone or shell are formed
In, while the transition zone or shell are performed etching using inorganic acid.
Further, the halogen inorganic salt is preferably halogen zinc salt.
Further, halogen contained by the halogen inorganic salt includes F, Cl or Br etc..
Further, the halogen inorganic salt is preferably ZnCl2。
The inorganic salts that inorganic acid lithographic method of the present invention is protected are not limited only to the nothing employed in embodiment
Machine salt.
The present invention preferentially using the purpose of the halogen inorganic salt of Zn classes be its can be during the reaction to be formed ZnSe or
Person ZnSeS or ZnS provide Zn ions, later stage halide ion and H+It can be removed in quantum later purification after forming inorganic acid,
It can also vapor away at high temperature.
The H that the present invention is provided using halide anion with amine in reaction system+In conjunction with the corresponding inorganic acid of production
(HF, HCl, HBr) performs etching quantum dot core, transition zone or shell, can remove the defect of quantum dot, improves quantum dot
Luminous mass.
Among certain preferred embodiments, the lithographic method includes：
Make the hybrid reaction system comprising indium source, zinc source, ligand solvent and non-coordinating solvent react in 150~200 DEG C 1~
30min obtains indium presoma and zinc precursor mixed liquor；
Phosphine source is added into the hybrid reaction system in 200~300 DEG C and forms quantum dot core InP and/or InZnP；
The quantum dot core is performed etching with inorganic acid.
Further, the time of the etching is 0.5~20h, preferably 0.5~2h.
Further, the molar ratio in the indium source and zinc source is 0.01：1~1：1.
Further, the indium source includes in indium acetate, inidum chloride, tetradecylic acid indium, indium iodide, indium bromide and indium oxide etc.
Any one or two or more combinations, preferably inidum chloride, but not limited to this.
Further, the zinc source includes zinc chloride, zinc bromide, zinc iodide, zinc stearate, zinc acetate, zinc oleate and ten
Any one in tetracid zinc etc. or two or more combinations, preferably zinc stearate, but not limited to this.
Further, the phosphine source is as anion ligand comprising three (dimethylamino) phosphines, three (diethylin) phosphines,
Any one in three (trimethylsilyl) phosphines etc. or two or more combinations, preferably three (dimethylamino) phosphines and three (two
Ethylamino-) phosphine etc., but not limited to this.
Further, the ligand solvent include amount of carbon atom >=5 saturated fatty acid and/or unsaturated fatty acid,
In saturated amine compounds of amount of carbon atom >=6 and/or unsaturated aminated compounds etc. any one or it is two or more
Combination, such as can be tetradecylic acid, oleic acid, stearic acid, oleyl amine, di-n-propylamine, n-hexylamine, n-octyl amine, trioctylamine, eight amine, 12
Any one in amine, octadecylamine, cetylamine and tetradecy lamine etc. or two or more combinations, however, it is not limited to this.
Further, the non-coordinating solvent include the alkane derivatives of amount of carbon atom >=10, alkenes compounds,
Any one in ether compound and aromatic compound etc. or two or more combinations, such as it includes 18 that can be
Any one in alkene, 19 alkene, icosa alkene, lignocerane, docosane, eicosane, octadecane and atoleine etc. or two
Kind or more combination, however, it is not limited to this.
Further, the molar ratio in the combination of the indium presoma and zinc precursor and anion ligand phosphine source is 0.1：1
~1：1.
Among certain preferred embodiments, the lithographic method includes：In the completion first step or to the amount
After the etching of son point core, selenium source, zinc source, the sulphur source for selectively adding or being added without and choosing are added into the hybrid reaction system
Selecting property is added or the inorganic salts that are added without, and reacts 1~60min in 150~300 DEG C, in coating ZnSe on the quantum dot core
Transition zone and/or ZnSeS layers, or it is performed etching while coating the ZnSe transition zones and/or ZnSeS layers.
Further, the selenium source includes tri octyl phosphine selenium, tributylphosphine selenium, selenium-octadecylene solution and selenium-oleyl amine solution
Any one in or two or more combinations, preferably tri octyl phosphine selenium, but not limited to this.
Further, the zinc source includes zinc stearate, zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc oleate and ten
Any one in tetracid zinc etc. or two or more combinations, preferably zinc stearate, but not limited to this.
Further, the sulphur source includes tri octyl phosphine sulphur, tributylphosphine sulphur, sulphur-octadecylene solution, sulphur-oleyl amine solution
Any one in the mercaptan compound etc. for being R-SH with chemical formula or two or more combinations, preferably tributylphosphine sulphur,
Middle R is the alkyl of carbon atom number >=6, but not limited to this.
Further, the molar ratio of the selenium source, zinc source and sulphur source is 0.1：1：0~1：1：1, preferably 0.5：1：0~
0.5：1：0.5.
Among certain preferred embodiments, the lithographic method includes：In the completion second step or to described
After ZnSe transition zones and/or ZnSeS layers of etching, sulphur source, zinc source are added into the hybrid reaction system and selectively adds
Or the inorganic salts being added without, and 1~60min, preferably 20~40min are reacted in 280~320 DEG C, in the ZnSe transition zones
And/or ZnS shells are coated on ZnSeS layers or it is performed etching while coating the ZnS shells.It is molten that inorganic acid is added
The stable quantum-dot structure of the further growth of liquid etching.
Further, the sulphur source includes tri octyl phosphine sulphur, tributylphosphine sulphur, sulphur-octadecylene solution, sulphur-oleyl amine solution
Any one in the mercaptan compound etc. for being R-SH with chemical formula or two or more combinations, wherein R are carbon atom number >=6
Alkyl, preferably n- dodecyl mereaptan, tri octyl phosphine sulphur etc., but not limited to this.
Further, the zinc source includes zinc stearate, zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc oleate and second
Any one in base xanthic acid zinc etc. or two or more combinations, preferably zinc stearate, but not limited to this.
Further, the sulphur source and the molar ratio in zinc source are 0.1：1~1：1.
Among certain preferred embodiments, the lithographic method further includes：In the completion third step or to described
After the etching of ZnS shells, into the hybrid reaction system, addition chemical formula is the mercaptan compound of R-SH in 200~300 DEG C
1~60min is reacted, quantum dot is obtained, wherein R is the alkyl of carbon atom number >=6.
The present invention etching principle be：The H provided using amine in halide anion and reaction system+In conjunction with production pair
The inorganic acid (HF, HCl, HBr) answered, performs etching quantum dot core, transition zone or shell, removes the defect of quantum dot, improves
The luminous mass of quantum dot.It the advantage is that and just quantum dot is etched in the synthesis process, eliminate quantum dot and closing
At anisotropy in the process, woth no need to by quantum dot it is synthetic after etch again, and the amount of the acid formed in its etching can
With control, i.e. etching is controllable.
The other side of the embodiment of the present invention additionally provides the quantum dot synthesized by preceding method.The knot of the quantum dot
Structure is stablized, and optics, chemically and thermally stability is excellent.
Further, the emission peak wave band of the quantum dot is adjustable, and emission peak half-peak breadth is less than 45nm, and luminous efficiency is more than
70%.
By above-mentioned technical proposal, the present invention performs etching quantum dot using inorganic acid, both participates in the synthesis process
Synthetic reaction is completed to etch to quantum dot again, eliminates the anisotropy of quantum dot in the synthesis process, woth no need to by quantum dot
It is etched again after synthetic, method is safer, and the amount of the acid formed in its etching can control, not only can the amount of raising
The fluorescence quantum yield of son point, can also improve its optics, chemically and thermally stability, obtain the stable quantum dot knot of growth
Structure.
Technical scheme of the present invention is described in further details with reference to embodiment and attached drawing, but the present invention and not only
It is limited only to following embodiments.
The preparation method for some reaction reagents that following embodiment uses is as follows, but is suitable for the invention reagent not
It is confined to this：
Presoma is prepared：
Zinc etching liquid drives body and configures (ZnCl2/OLAM 0.5mmol/ml)
Zinc chloride ZnCl220mmol Alpha reagent 98%
Oleyl amine OLAM 40ml Aladdins 90%
Above-mentioned raw materials are placed in 250ml three-neck flasks and are warming up to 50 DEG C of dissolvings, under argon atmosphere.
Zinc stearate solution preparation method (Zn (st/)2ODE 1mmol/ml)
Zinc stearate Zn (st)250mmol Aladdins 20%
Octadecylene ODE 50ml Alpha reagent 90%
Above-mentioned raw materials are placed in 250ml three-neck flasks be warming up to 120 DEG C be evacuated to bubble-free after, obtain water white transparency
It is spare after being cooled to 80 DEG C after solution.
Indium precursor solution configures (In/OLAM 0.5mmol/ml)
Inidum chloride InCl35mmol Aladdins 99.99%
Oleyl amine OLAM 20ml Aladdins 90%
Above-mentioned raw materials are placed in 100ml three-neck flasks be warming up to 120 DEG C be evacuated to bubble-free after, obtain water white transparency
It is spare after being cooled to 80 DEG C after solution.
Tri octyl phosphine selenium preparation method (TOPSe 2M)
Tri octyl phosphine TOP 20ml Alpha reagent 90%
Selenium powder 4mmol Alpha reagent 99.999%
Above-mentioned raw materials are placed in 100ml three-neck flasks, be warming up to 120 DEG C be evacuated to bubble-free after obtain water white transparency
After solution, it is spare to be cooled to room temperature.
Tri octyl phosphine sulphur preparation method (TOPS 2M)
Tri octyl phosphine TOP 20ml Alpha reagent 90%
Sulphur powder 4mmol Alpha reagent 99.999%
Above-mentioned raw materials are placed in 100ml three-neck flasks, be warming up to 120 DEG C be evacuated to bubble-free after obtain water white transparency
After solution, it is spare to be cooled to room temperature.
Embodiment 1 (quantum dot core etching)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder,
OLAM 5ml, ODE 5ml are warming up to 150 DEG C of reaction 30min, argon atmosphere, wherein indium source and zinc stearate Zn (st)2Rub
You are than being 0.01：1；
2,200 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) reaction 10min formation InP or InZnP quantum
Point core, is added ZnCl2/ OLAM 2ml react 30min, wherein the molar ratio of the combination and phosphine source of indium presoma and zinc precursor
It is 0.1：1；
3, TOPSe 1.5ml, Zn (st) is added2/ ODE 12ml react 30min, wherein TOPSe and Zn (st) at 280 DEG C2
Molar ratio be 0.1：1；
4, TOPS 1.5ml, Zn (st) is added2/ ODE 12ml react 20min, wherein TOPS and Zn (st) at 280 DEG C2's
Molar ratio is 0.1：1；
5, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 280 DEG C and obtains final product.
Embodiment 2 (quantum dot core etching)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder,
OLAM 5ml, ODE 5ml are warming up to 200 DEG C of reaction 1min, argon atmosphere, wherein indium source and zinc stearate Zn (st)2Mole
Than being 1：1；
2,300 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) reaction 10min formation InP or InZnP quantum
Point core, is added ZnCl2/ OLAM 2ml react 20h, wherein the combination of indium presoma and zinc precursor and the molar ratio in phosphine source are
1：1；
3, TOPSe, Zn (st) is added2/ ODE reacts 1min, wherein TOPSe and Zn (st) at 300 DEG C2Molar ratio be
0.5：1；
4, TOPS, Zn (st) is added2/ ODE reacts 1min, wherein TOPS and Zn (st) at 320 DEG C2Molar ratio be 0.5：
1；
5, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 300 DEG C and obtains final product.
Embodiment 3 (quantum dot core etching)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder,
OLAM 5ml, ODE 5ml are warming up to 200 DEG C, argon atmosphere, wherein indium source and zinc stearate Zn (st)2Molar ratio be 0.1：
1；
2,250 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) reaction 10min formation InP or InZnP quantum
Point core, is added ZnCl2/ OLAM 2ml react 2h, wherein the combination of indium presoma and zinc precursor and the molar ratio in phosphine source are
0.5：1；
3, TOPSe, Zn (st) is added2/ ODE reacts 30min, wherein TOPSe and Zn (st) at 250 DEG C2Molar ratio be
1：1；
4, TOPS 1.5ml, Zn (st) is added2/ ODE 12ml react 30min, wherein TOPS and Zn (st) at 300 DEG C2's
Molar ratio is 1：1；
5, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 290 DEG C and obtains final product.
Embodiment 4 (transition zone etching)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder
10mmol, OLAM 5ml, ODE 5ml are warming up to 180 DEG C of reaction 10min, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 1ml reaction 10min formation InP or InZnP amounts
Son point core；
3, TOPSe 1.5ml, Zn (st) is added2/ ODE 4ml, ZnCl2/ OLAM 2ml react 30min at 280 DEG C；
4, the operation of repetition step 32 times；
5, TOPS 1.5ml, Zn (st) is added2/ ODE 12ml react 20min at 300 DEG C；
6, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 300 DEG C and obtains final product.
Products therefrom solution is precipitated using ethyl alcohol, normal heptane, is dispersed in the normal heptane of 50ml after purification.It obtains after tested
Data wavelength PL is 523nm, and half-peak breadth Fwhm is 43nm, and quantum efficiency QY is 68%.
Embodiment 5 (transition zone etching)
1, in 100ml three-necked flasks, In/OLAM solution 20ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder
10mmol, OLAM 10ml, ODE 15ml are warming up to 160 DEG C of reaction 20min, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 2ml reaction 10min formation InP or InZnP amounts
Son point core；
3, TOPSe 3ml, Zn (st) is added2/ ODE 8ml, ZnCl2/ OLAM 4ml react 60min at 150 DEG C；
4, the operation of repetition step 32 times；
5, TOPS 3ml, Zn (st) is added2/ ODE 20ml react 60min at 300 DEG C；
6, it is added after n- dodecyl mereaptan (DDT) 3ml reacts 60min at 200 DEG C and obtains final product.
Embodiment 6 (transition zone etching) forms ZnSeS
1, in 100ml three-necked flasks, In/OLAM solution 20ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder
10mmol, OLAM 10ml, ODE 15ml are warming up to 180 DEG C of reaction 10min, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 2ml reaction 10min formation InP or InZnP amounts
Son point core；
3, the mixed liquor of TOPSe 1.5ml and TOPS 1.5ml, Zn (st) is added2/ ODE 8ml form ZnSeS, are added
ZnCl2/ OLAM 4ml react 30min at 280 DEG C；
4, the operation of repetition step 32 times；
5, TOPS 3ml, Zn (st) is added2/ ODE 20ml react 40min at 300 DEG C；
6, it is added after n- dodecyl mereaptan (DDT) 3ml reacts 20min at 300 DEG C and obtains final product.
Embodiment 7 (outermost shell etching)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder
2mmol, OLAM 5ml, ODE 5ml are warming up to 200 DEG C of reaction 1min, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 1ml reaction 10min formation InP or InZnP amounts
Son point core；
3, TOPSe 1.5ml, Zn (st) is added2/ ODE 12ml react 30min at 280 DEG C；
4, TOPS 0.5ml, ZnCl is added2/ OLAM 2ml, Zn (st)2/ ODE 4ml react 20min at 280 DEG C；
5, the operation of repetition step 42 times；
6, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 300 DEG C and obtains final product.
Embodiment 8 (successively all etchings)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder
2mmol, OLAM 5ml, ODE 5ml are warming up to 150 DEG C, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 1ml reaction 10min formation InP or InZnP amounts
Son point core, is added ZnCl2/ OLAM 2ml react 60min；
3, TOPSe 0.5ml, Zn (st) is added2/ ODE 4ml, ZnCl2/ OLAM 2ml react 30min at 280 DEG C；
4, the operation of repetition step 32 times；
5, TOPS 0.5ml, ZnCl is added2/ OLAM 2ml, Zn (st)2/ ODE 4ml react 20min at 290 DEG C；
6, the operation of repetition step 52 times；
7, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 300 DEG C and obtains final product.
Embodiment 9 (successively all etchings)
1, in 100ml three-necked flasks, In/OLAM solution 1ml, the zinc stearate Zn (st) of above-mentioned preparation is added2Powder
2mmol, OLAM 5ml, ODE 5ml are warming up to 180 DEG C of reaction 10min, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 1ml reaction 10min formation InP or InZnP amounts
Son point core, is added ZnCl2/ OLAM 2ml react 10h；
3, TOPSe 0.5ml, Zn (st) is added2/ ODE 4ml, ZnCl2/ OLAM 2ml react 30min at 280 DEG C；
4, the mixed liquor of TOPSe 1.5ml and TOPS 1.5ml, Zn (st) is added2/ ODE 8ml form ZnSeS, are added
ZnCl2/ OLAM 4ml react 30min at 280 DEG C；
5, the operation of repetition step 42 times；
6, TOPS 0.5ml, ZnCl is added2/ OLAM 2ml, Zn (st)2/ ODE 4ml react 20min at 290 DEG C；
7, the operation of repetition step 62 times；
8, it is added after n- dodecyl mereaptan (DDT) 2ml reacts 20min at 300 DEG C and obtains final product.
The present invention the obtained quantum dot of one exemplary embodiments is characterized, TEM pictures are as shown in Fig. 2, its indium phosphide core
The launching light spectrogram of shell is as shown in Figure 1.
Reference examples 1
1, in 100ml three-necked flasks, In/OLAM the solution 1ml, zinc stearate Zn (st) of above-mentioned preparation is added2Powder
2mmol, OLAM 5ml, ODE 5ml are warming up to 100 DEG C, argon atmosphere；
2,220 DEG C are warming up to, three (dimethylamino) phosphine (P (EDA) are added3) 1ml reaction 10min formation In (Zn) P quantum
Point core, reacts 10min, is etched using the hydrofluoric acid (HF) of various concentration, takes solution 5ml tests after purification respectively；
3, TOPSe 1.5ml, Zn (st) is added2/ ODE 12ml react 30min at 280 DEG C；
4, TOPS 1.5ml, Zn (st) is added2/ ODE 12ml react 20min；
5, final product is obtained after n- dodecyl mereaptan (DDT) 2ml reactions 20min is added.
Products therefrom solution is precipitated using ethyl alcohol, normal heptane, is dispersed in the normal heptane of 50ml after purification.It obtains after tested
Data such as table 1.
The test result of 1 reference examples of table, 1 obtained quantum dot
Reference examples 2
This reference examples and reference examples 1 are almost the same, the difference is that：Using nitric acid (HNO3) etching, purification is taken respectively
Solution 5ml is tested afterwards, and the results are shown in Table 2.
The test result of 2 reference examples of table, 1 obtained quantum dot
By Tables 1 and 2 it is found that being performed etching with hydrofluoric acid and nitric acid, quantum dot occurs not as the time increases it
Stabilization is quenched therewith although brightness is promoted.
In conclusion by above-mentioned technical proposal, the present invention carries out quantum dot using the inorganic acid containing halogens
Etching had not only participated in synthetic reaction and has completed etching to quantum dot again in the synthesis process, eliminated quantum dot in the synthesis process
Anisotropy, woth no need to by quantum dot it is synthetic after etch again, method is safer, and its etching formed in acid amount
It can control, can not only improve the fluorescence quantum yield of quantum dot, its optics, chemically and thermally stability can also be improved,
Obtain the stable quantum-dot structure of growth.
In addition, mode of the inventor referring also to embodiment 1- embodiments 9, with the other raw materials listed in this specification
It is tested with condition etc., for example, replacing inidum chloride system using indium acetate, tetradecylic acid indium, indium iodide, indium bromide and indium oxide
Standby indium source replaces zinc stearate as zinc source using zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc oleate and tetradecylic acid zinc,
Replace three (dimethylamino) phosphines as phosphine source using three (diethylin) phosphines, three (trimethylsilyl) phosphines, using tributylphosphine
Selenium, selenium-octadecylene solution and selenium-oleyl amine solution replace tri octyl phosphine selenium as selenium source, using tributylphosphine sulphur, sulphur-octadecylene
Solution, sulphur-oleyl amine solution and chemical formula replace tri octyl phosphine sulphur obtained as sulphur source, and equally by the mercaptan compound of R-SH
Emission peak wave band is adjustable, half-peak width, and luminous efficiency is high, the quantum-dot structure that optics, chemically and thermally stability are stablized.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, its object is to allow be familiar with this
The personage of item technology cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.Example
Such as, the part that do not address in the present specification is taken or is used for reference prior art and can be realized, therefore all according to spirit of that invention reality
Equivalent change or modification made by matter, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of quantum dot, including：It synthesizes the first step of quantum dot core, coated at least in the quantum dot core
The second step of one transition zone, and, the third step of shell is coated on the transition zone；Characterized by further comprising：
In first step, quantum dot core is performed etching with inorganic acid；And/or in the second step, with inorganic acid to an at least transition
Layer performs etching；And/or in third step, shell is performed etching with inorganic acid；Wherein, the halogen contained by the inorganic acid
Plain anion, H+Halogen inorganic salt, the amine being respectively derived from the reaction system of first step, second step or third step
Substance.
2. synthetic method according to claim 1, it is characterised in that：The halogen inorganic salt includes halogen zinc salt；It is preferred that
, halogen includes F, Cl or Br contained by the halogen inorganic salt；Especially preferred, the halogen inorganic salt includes ZnCl2。
3. synthetic method according to claim 1, it is characterised in that including：
Make the hybrid reaction system comprising indium source, zinc source, ligand solvent and non-coordinating solvent react in 150~200 DEG C 1~
30min obtains indium presoma and zinc precursor mixed liquor；
Phosphine source is added into the hybrid reaction system in 200~300 DEG C and forms quantum dot core InP and/or InZnP；
The quantum dot core is performed etching with inorganic acid；Preferably, the time of the etching be 0.5~20h, preferably 0.5
~2h.
4. synthetic method according to claim 3, it is characterised in that：The molar ratio in the indium source and zinc source is 0.01：1~
1：1；Preferably, the indium source includes any one in indium acetate, inidum chloride, tetradecylic acid indium, indium iodide, indium bromide and indium oxide
Kind or two or more combinations, preferably inidum chloride；
And/or the zinc source includes in zinc chloride, zinc bromide, zinc iodide, zinc stearate, zinc acetate, zinc oleate and tetradecylic acid zinc
Any one or two or more combinations, preferably zinc stearate；
And/or the phosphine source includes appointing in three (dimethylamino) phosphines, three (diethylin) phosphines, three (trimethylsilyl) phosphines
Meaning a combination of one or more, preferably three (dimethylamino) phosphines.
5. synthetic method according to claim 3, it is characterised in that：The ligand solvent includes amount of carbon atom >=5
Saturated fatty acid and/or unsaturated fatty acid, the saturated amine compound of amount of carbon atom >=6 and/or unsaturated amine chemical combination
Any one in object or two or more combinations；Preferably, the ligand solvent includes tetradecylic acid, oleic acid, stearic acid, oil
Any one in amine, di-n-propylamine, n-hexylamine, n-octyl amine, trioctylamine, eight amine, lauryl amine, octadecylamine, cetylamine and tetradecy lamine
Or two or more combination；And/or the non-coordinating solvent includes the alkane derivative of amount of carbon atom >=10, olefines
Any one in compound, ether compound and aromatic compound or two or more combinations；Preferably, described non-to match
Position solvent includes in octadecylene, 19 alkene, icosa alkene, lignocerane, docosane, eicosane, octadecane and atoleine
Any one or two or more combinations.
6. synthetic method according to claim 3, it is characterised in that：Combination and the phosphine of the indium presoma and zinc precursor
The molar ratio in source is 0.1：1~1：1.
7. synthetic method according to claim 1, it is characterised in that including：In the completion first step or to the amount
After the etching of son point core, selenium source, zinc source, the sulphur source for selectively adding or being added without and choosing are added into the hybrid reaction system
Selecting property is added or the inorganic salts that are added without, and reacts 1~60min in 150~300 DEG C, in coating ZnSe on the quantum dot core
Transition zone and/or ZnSeS layers, or it is performed etching while coating the ZnSe transition zones and/or ZnSeS layers；It is excellent
Choosing, the selenium source includes any one in tri octyl phosphine selenium, tributylphosphine selenium, selenium-octadecylene solution and selenium-oleyl amine solution
Or two or more combinations, preferably tri octyl phosphine selenium；Preferably, the zinc source include zinc chloride, it is zinc bromide, zinc iodide, hard
Any one in resin acid zinc, zinc acetate, zinc oleate and tetradecylic acid zinc or two or more combinations, preferably zinc stearate；It is excellent
Choosing, the sulphur source includes that tri octyl phosphine sulphur, tributylphosphine sulphur, sulphur-octadecylene solution, sulphur-oleyl amine solution and chemical formula are R-
Any one in the mercaptan compound of SH or two or more combinations, preferably tributylphosphine sulphur, wherein R be carbon atom number >=
6 alkyl；Preferably, the molar ratio of the selenium source, zinc source and sulphur source is 0.1：1：0~1：1：1, preferably 0.5：1：0~
0.5：1：0.5.
8. synthetic method according to claim 1, it is characterised in that including：In the completion second step or to described
After ZnSe transition zones and/or ZnSeS layers of etching, sulphur source, zinc source are added into the hybrid reaction system and selectively adds
Or the inorganic salts being added without, and 1~60min, preferably 20~40min are reacted in 280~320 DEG C, in the ZnSe transition zones
And/or ZnS shells are coated on ZnSeS layers or it is performed etching while coating the ZnS shells；Preferably, described
Sulphur source includes that tri octyl phosphine sulphur, tributylphosphine sulphur, sulphur-octadecylene solution, sulphur-oleyl amine solution and chemical formula are the Thiolation of R-SH
Any one in object or two or more combinations, preferably n- dodecyl mereaptan and/or tri octyl phosphine sulphur are closed, wherein R is that carbon is former
The alkyl of subnumber >=6；Preferably, the zinc source includes zinc stearate, zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc oleate
With any one or the two or more combinations in xanthopone, preferably zinc stearate；Preferably, the sulphur source and zinc
The molar ratio in source is 0.1：1~1：1.
9. according to the synthetic method described in any one of claim 1-8, it is characterised in that further include：Complete the third step
It is rapid or to the etching of the ZnS shells after, be added into the hybrid reaction system mercaptan compound that chemical formula is R-SH in
200~300 DEG C of 1~60min of reaction, obtain quantum dot, and wherein R is the alkyl of carbon atom number >=6.
10. the emission peak wave band of the quantum dot synthesized by any one of claim 1-9 the methods, the quantum dot is adjustable,
Emission peak half-peak breadth is less than 45nm, and luminous efficiency is more than 70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810586981.0A CN108641720A (en) | 2018-06-08 | 2018-06-08 | A kind of quantum dot and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810586981.0A CN108641720A (en) | 2018-06-08 | 2018-06-08 | A kind of quantum dot and its synthetic method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108641720A true CN108641720A (en) | 2018-10-12 |
Family
ID=63751986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810586981.0A Pending CN108641720A (en) | 2018-06-08 | 2018-06-08 | A kind of quantum dot and its synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108641720A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175615A (en) * | 2020-10-14 | 2021-01-05 | 苏州星烁纳米科技有限公司 | Preparation method of quantum dots, quantum dot film and display device |
| EP3786258A1 (en) * | 2019-08-29 | 2021-03-03 | Samsung Electronics Co., Ltd. | Quantum dots and device including the same |
| CN113061436A (en) * | 2021-03-04 | 2021-07-02 | 苏州星烁纳米科技有限公司 | Electro-cadmium-free quantum dot, preparation method thereof and light emitting diode |
| CN113105884A (en) * | 2021-02-09 | 2021-07-13 | 深圳扑浪创新科技有限公司 | Quantum dot and preparation method and application thereof |
| WO2021195882A1 (en) * | 2020-03-30 | 2021-10-07 | 京东方科技集团股份有限公司 | Quantum dot structure and manufacturing method therefor, and quantum dot light-emitting device |
| CN115232622A (en) * | 2022-08-24 | 2022-10-25 | 合肥福纳科技有限公司 | Preparation method of non-Cd quantum dots and non-Cd quantum dots prepared by same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765649A (en) * | 2007-07-31 | 2010-06-30 | 纳米技术有限公司 | nanoparticles |
| CN106479482A (en) * | 2016-09-20 | 2017-03-08 | 纳晶科技股份有限公司 | Inp quantum dot and preparation method thereof |
| CN106701059A (en) * | 2016-11-11 | 2017-05-24 | 纳晶科技股份有限公司 | InP quantum dot and preparation method therefor |
| CN106987250A (en) * | 2017-01-16 | 2017-07-28 | 中国药科大学 | The preparation of the InP quantum dots of near-infrared fluorescent transmitting |
-
2018
- 2018-06-08 CN CN201810586981.0A patent/CN108641720A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765649A (en) * | 2007-07-31 | 2010-06-30 | 纳米技术有限公司 | nanoparticles |
| CN106479482A (en) * | 2016-09-20 | 2017-03-08 | 纳晶科技股份有限公司 | Inp quantum dot and preparation method thereof |
| CN106701059A (en) * | 2016-11-11 | 2017-05-24 | 纳晶科技股份有限公司 | InP quantum dot and preparation method therefor |
| CN106987250A (en) * | 2017-01-16 | 2017-07-28 | 中国药科大学 | The preparation of the InP quantum dots of near-infrared fluorescent transmitting |
Non-Patent Citations (2)
| Title |
|---|
| PARTHIBAN RAMASAMY等: "Tunable, Bright, and Narrow-Band Luminescence from Colloidal Indium Phosphide Quantum Dots", 《CHEMISTRY OF MATERIALS》 * |
| S.ADAM等: "The effect of nanocrystal surface structure on the luminescence properties:Photoemission study of HF-etched InP nanocrystals", 《THE JOURNAL OF CHEMICAL PHYSICS》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3786258A1 (en) * | 2019-08-29 | 2021-03-03 | Samsung Electronics Co., Ltd. | Quantum dots and device including the same |
| CN112442371A (en) * | 2019-08-29 | 2021-03-05 | 三星电子株式会社 | Quantum dot, manufacturing method thereof, quantum dot group comprising quantum dot, and electroluminescent device |
| CN112442371B (en) * | 2019-08-29 | 2024-04-12 | 三星电子株式会社 | Quantum dot, method of manufacturing the same, quantum dot group including the same, and electroluminescent device |
| US11499098B2 (en) | 2019-08-29 | 2022-11-15 | Samsung Electronics Co., Ltd. | Quantum dots and device including the same |
| WO2021195882A1 (en) * | 2020-03-30 | 2021-10-07 | 京东方科技集团股份有限公司 | Quantum dot structure and manufacturing method therefor, and quantum dot light-emitting device |
| CN113795566A (en) * | 2020-03-30 | 2021-12-14 | 京东方科技集团股份有限公司 | Quantum dot structure, manufacturing method thereof and quantum dot light-emitting device |
| CN113795566B (en) * | 2020-03-30 | 2024-04-09 | 京东方科技集团股份有限公司 | Quantum dot structure, manufacturing method thereof and quantum dot light-emitting device |
| CN112175615B (en) * | 2020-10-14 | 2023-07-11 | 苏州星烁纳米科技有限公司 | Quantum dot preparation method, quantum dot film and display device |
| CN112175615A (en) * | 2020-10-14 | 2021-01-05 | 苏州星烁纳米科技有限公司 | Preparation method of quantum dots, quantum dot film and display device |
| CN113105884A (en) * | 2021-02-09 | 2021-07-13 | 深圳扑浪创新科技有限公司 | Quantum dot and preparation method and application thereof |
| CN113061436A (en) * | 2021-03-04 | 2021-07-02 | 苏州星烁纳米科技有限公司 | Electro-cadmium-free quantum dot, preparation method thereof and light emitting diode |
| CN113061436B (en) * | 2021-03-04 | 2023-03-31 | 苏州星烁纳米科技有限公司 | Electro-cadmium-free quantum dot, preparation method thereof and light emitting diode |
| CN115232622B (en) * | 2022-08-24 | 2023-06-06 | 合肥福纳科技有限公司 | Preparation method of non-Cd quantum dot and prepared non-Cd quantum dot |
| CN115232622A (en) * | 2022-08-24 | 2022-10-25 | 合肥福纳科技有限公司 | Preparation method of non-Cd quantum dots and non-Cd quantum dots prepared by same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108641720A (en) | A kind of quantum dot and its synthetic method | |
| CN106701059B (en) | InP quantum dot and preparation method thereof | |
| TWI805548B (en) | Quantum dot material and manufacturing method of quantum dot material | |
| Wang et al. | Synthesis of Mn-doped ZnS microspheres with enhanced visible light photocatalytic activity | |
| Sun et al. | Highly luminescent, stable, transparent and flexible perovskite quantum dot gels towards light-emitting diodes | |
| JP6483716B2 (en) | Quantum dot nanoparticles with improved stability and luminous efficiency | |
| JP2017512245A (en) | Cadmium-free quantum dot nanoparticles | |
| CN108822856B (en) | Semiconductor nanocrystals and methods of making the same | |
| CN110157407A (en) | InP quantum dot and preparation method thereof | |
| CN110506096A (en) | Iii-v quantum dot and preparation method thereof | |
| CN108699434A (en) | INP quantum dots and its manufacturing method with GaP and AlP shells | |
| US20070049765A1 (en) | Process for producing semiconductor nanocrystal cores, core-shell, core-buffer-shell, and multiple layer systems in a non-coordinating solvent utilizing in situ surfactant generation | |
| CN106024999B (en) | A kind of quantum dot surface method of purification improving perovskite LED luminous efficiency | |
| JP2016196631A (en) | PROCESS FOR INCREASING PHOTOLUMINESCENCE INTERNAL QUANTUM EFFICIENCY OF NANOCRYSTAL, IN PARTICULAR OF AgInS2-ZnS NANOCRYSTAL | |
| CN108690600A (en) | High pressure prepares the method and quantum dot of quantum dot | |
| Andres-Penares et al. | Quantum size confinement in gallium selenide nanosheets: band gap tunability versus stability limitation | |
| Chen et al. | Room-temperature ionic-liquid-assisted hydrothermal synthesis of Ag-In-Zn-S quantum dots for WLEDs | |
| CN108587628B (en) | Synthesis method of quantum dots | |
| He et al. | Controlled synthesis of quantum confined CsPbBr3 perovskite nanocrystals under ambient conditions | |
| Yang et al. | Suppressing ion migration of CsPbBr x I3-x nanocrystals by Nickel doping and the application in high-efficiency WLEDs | |
| Zhang et al. | Deep-red emissive colloidal lead-based triiodide perovskite/telluride nanoscale heterostructures with reduced surface defects and enhanced stability for indoor lighting applications | |
| Mei et al. | Silica encapsulation of metal perovskite nanocrystals in a photoluminescence type display application | |
| Shu et al. | Highly efficient and blue-emitting CsPbBr3 quantum dots synthesized by two-step supersaturated recrystallization | |
| CN112980428B (en) | Core-shell structure quantum dot, preparation method and application thereof | |
| Xie et al. | Complementary ligand decorated cesium lead bromide nanoplatelets for high performance light-emitting diodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181012 |
|
| RJ01 | Rejection of invention patent application after publication |