CN107384406A - A kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots - Google Patents
A kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots Download PDFInfo
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- CN107384406A CN107384406A CN201710736800.3A CN201710736800A CN107384406A CN 107384406 A CN107384406 A CN 107384406A CN 201710736800 A CN201710736800 A CN 201710736800A CN 107384406 A CN107384406 A CN 107384406A
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- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical group [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002096 quantum dot Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
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- 239000000843 powder Substances 0.000 claims description 6
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 210000004209 hair Anatomy 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011257 shell material Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000011258 core-shell material Substances 0.000 abstract description 9
- 239000011824 nuclear material Substances 0.000 abstract description 5
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- 239000011701 zinc Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- -1 octadecylene Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical class [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910003363 ZnMgO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DIWNCNINVWYUCD-UHFFFAOYSA-N acetyl acetate;zinc Chemical compound [Zn].CC(=O)OC(C)=O DIWNCNINVWYUCD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- ZTSAVNXIUHXYOY-CVBJKYQLSA-L cadmium(2+);(z)-octadec-9-enoate Chemical compound [Cd+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O ZTSAVNXIUHXYOY-CVBJKYQLSA-L 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
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- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004054 semiconductor nanocrystal Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
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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
- C09K11/08—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
- H01L33/26—Materials of the light emitting region
- H01L33/28—Materials of the light emitting region containing only elements of Group II and Group VI of the Periodic Table
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Abstract
The present invention relates to a kind of anti-I type core/shell structure CdZnS/CdSe quantum dot preparation methods, together with the Combination of Methods for adsorbing the semi-conducting material CdZnS of different band gap and CdSe quantum dot by continuous ionic layer, formed using CdZnS as nuclear material, the core/shell structure quantum dot using CdSe as Shell Materials.CdZnS/CdSe quantum dots prepared by the present invention can by continuously coat different-thickness, the different numbers of plies CdSe shells, obtain the wide spectral range of continuously adjustable, have the characteristics that monochromaticjty is good, monodispersity is good and luminescent spectrum is symmetrical, especially possess the optical characteristics not available for independent CdZnS and CdSe quantum dot under identical size；The CdSe shells of other different-thickness determine the distribution of whole core shell structure electron hole, and the material of various different application properties can be flexibly prepared with this characteristic.
Description
Technical field
The present invention relates to the preparation of nanocrystalline material and application, for a kind of anti-I type CdZnS/CdSe core/shell structure quantum
The preparation method and LED light-emitting display devices of point.
Background technology
Nanoscale structures material abbreviation nano material, refer to the size of construction unit between 1 nanometer~100 nanometer ranges it
Between.Because its size is already close to the coherence length of electronics, its property is because the property that strong relevant caused self-organizing is
Matter changes a lot.Also, its yardstick has the special effects of large surface plus it, therefore already close to the wavelength of light
Its characteristic showed, such as fusing point, magnetic, optics, heat conduction, conductive characteristic, often different from the integrality of the material
It is showed property.The present invention is to make use of the optics and conductive characteristic of nano material.
Quantum dot is also known as semiconductor nanocrystal, is stimulated by light or electricity, can send coloured light, the color of light by
The composition and size of quantum dot determine.Quantum dot is a kind of nano particle being made up of II-VI race or III-group Ⅴ element.
Particle diameter is typically in the range of between 1-10nm, and because electronics and hole are by quantum confinement, continuous band structure becomes special with molecule
The discrete energy level structure of property, can launch fluorescence after being excited.Based on quantum effect, quantum dot solar cell, luminescent device, light
The fields such as biomarker are with a wide range of applications.Quantum dot can be manufactured by many different methods at present, in advance
Phase, this material had great application potential in the nanoelectronics of 21st century.
The quantum dot of core shell structure is roughly divided into three classes, respectively I type, II type and anti-I type, each corresponds to respectively different
Core, the distribution of shell material band gap.The core shell structure CdZnS/CdSe quantum dots of the present invention are the CdZnS nuclear materials of broad-band gap by outer layer
The CdSe shell materials of narrow band gap are coated, and form the quantum dot of anti-I type core shell structure.The present invention is using hot injection method synthesis quantum
Point, the CdZnS/CdSe quantum dots of core shell structure are synthesized using the method for fractional steps, be then applied to quantum dot to make LED chip and too
In terms of positive energy battery, its excellent performance is further embodied.
The content of the invention
It is an object of the invention to provide a kind of preparation method of anti-I type core shell structure CdZnS/CdSe quantum dots,
CdZnS/CdSe quantum dots are prepared using high warm injection method, continuous ionic layer absorption method, and the quantum dot of preparation has substantially
Core shell structure, shell distribution can be widened to several layers by 1 layer, and the cladding of each layer of CdSe shell corresponds to the hair of a wave band
Light property；With the cladding of CdSe layers, the quantum yield of the quantum dot（QY）Tend to first raise the trend reduced afterwards；Specific shadow
The factor of sound need to be probed into.Prepared CdZnS/CdSe quantum dots have the narrow i.e. monochromaticjty of halfwidth is good, PL spectrum symmetrically i.e.
The features such as excellent luminance performance and continuously adjustabe wide spectrum that monodispersity waits well, and single CdZnS under identical size
The characteristic that CdZnS/CdSe quantum dots are showed after combining can not be showed with CdSe quantum dot, the CdZnS/CdSe after combination is created
The optical characteristics abundanter than single quantum dot.
The technical solution adopted by the present invention is as follows：A kind of preparation side of anti-I type CdZnS/CdSe core/shell structure quantum dots
Method, it is characterised in that method and step includes：
（1）Injection method is warmed by height first, then insulation synthesis CdZnS quantum dots；
（2）By the step（1）Obtained CdZnS quantum dots mix with corresponding ligand solvent is used as main reaction, then notes respectively
Enter, zwitterion is added dropwise is incubated to obtain CdZnS/CdSe nuclear shell structure quantum points.
The step（1）Middle Zn elements are excessive, and Zn and Cd mol ratio are 10:1.
The step（2）In be injected separately into, the order that is added dropwise zwitterion is first to inject anion, insulation 20 minutes it
Afterwards, then it is added dropwise cation.
The step（1）The CdZnS quantum dots of middle preparation need to be purified to obtain CdZnS powder, and purge process includes：
The CdZnS quantum dot stostes of the synthesis are mixed with n-hexane, multiple centrifuging and taking supernatant, remove unnecessary Zn elements, with
Supernatant is mixed with excess ethyl alcohol afterwards, centrifuged, and is dried in vacuo and obtains CdZnS quantum dot powder.
The step（1）The temperature of middle insulation is 310 DEG C, soaking time 10min.
The step（2）In the corresponding non-coordinating solvent that refers to be 1-ODE octadecylenes and oleyl amine.
The step（2）The drop rate of cationic is one drop/2-3s, and holding temperature is 220 DEG C, and soaking time is
20min。
A kind of a kind of LED light-emitting display devices of the preparation of described anti-I type CdZnS/CdSe core/shell structure quantum dots,
Including ITO electro-conductive glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electrode set gradually.Prepare
Method includes：By the method for spin coating by each layer successively spin-coating film, and each layer is all dried at a certain temperature, Ran Houzai
Electrode is prepared by the method for evaporation, is prepared into a complete LED light-emitting display device.The CdZnS/CdSe quantum prepared
Point will further apply LED, and the material and each material used in device act as ITO electro-conductive glass as core
The substrate of piece, ZnMgO is as electron transfer layer, and QDs quantum dots are as luminescent layer, PEDOT:PSS as hole injection layer,
Poly-TDP passes through glove box hot evaporation to the ITO conduction glass for having spun each several part material as hole transmission layer, Al materials
Electrode is used as on glass.A LED for applying CdZnS/CdSe quantum dots has thus been prepared, has further been passed through
Integrating sphere can test each item data so as to draw every excellent specific property of the quantum dot.
It is an advantage of the invention that：The CdZnS/CdSe quantum dots of preparation can be by continuously coating different-thickness, difference
The CdSe shells of the number of plies, obtain the wide spectral range of continuously adjustable, have that monochromaticjty is good, monodispersity is good and luminescent spectrum
The features such as symmetrical, especially possesses the optical characteristics not available for independent CdZnS and CdSe quantum dot under identical size；It is different in addition
The CdSe shells of thickness determine the distribution of whole core shell structure electron hole, flexibly can be prepared with this characteristic various
The material of different application property.Light-emitting diode display part based on quantum dot of the present invention compares single CdZnS and CdSe quantum dot LED
Device has the characteristics of high efficiency, stability is good.
Brief description of the drawings
Fig. 1 is that the pl of patent CdZnS/CdSe quantum dots of the present invention schemes.
Fig. 2 is the structure chart of patent light-emitting diode display part of the present invention.
Embodiment
The present invention a kind of preparation method and LED of anti-I type core shell structure CdZnS/CdSe quantum dots, specifically
Implementation steps are as follows：
1st, the preparation method of CdZnS/CdSe quantum dots：
（1）CdZnS nuclear materials are synthesized first, and cadmium oxide CdO and acetic anhydride zinc Zn (Ac) is respectively adopted in Cd and Zn2As former material
Material, mol ratio Zn:Cd=10:1, by 0.5mmolCdO in 50ml there-necked flasks（0.064g) with 5mmolZn (Ac)2
（0.917g）5ml oleic acid OA are mixed, 150 DEG C is heated to, to form zinc oleate and cadmium oleate, during which vacuumizes 40 points
Clock, it is necessary to carry out pumping inflation 3 times to main reaction before next step is carried out, to ensure to vacuumize completely；Subsequent applying argon gas,
10ml octadecylene 1-ODE are injected under ar gas environment, are heated to 300 DEG C, inject 1mmolS sources when temperature reaches 300 DEG C（It is high
Bright sulfur is dissolved in octadecylene 1-ODE）, reaction temperature is increased to 310 DEG C in last 10 minutes, end is now reacted and removes heating
Cover and cool, that is, form CdZnS nuclear materials.
（2）Before the synthesis of final material is carried out, it is essential that right（1）The CdZnS of middle synthesis carries out purification processes,
Unnecessary Zn elements and other impurities are removed, because if unnecessary Zn materials once be present in CdZnS nuclear quantum dots, when entering
During the cladding of row next step CdSe shells, CdZnS/ZnSe quantum dots, the unique complete phase of this and the present invention can be synthesized first
Run counter to.So the purification to CdZnS nuclear quantum dots is a vital step.The method of purification includes:First stoste carry out from
The heart, goes to precipitate, and is repeatedly centrifuged after appropriate n-hexane is added in supernatant, until not precipitated in the solution after centrifugation, needs here
It is important to note that（Stickyization can occur when stoste is down to room temperature, the present invention is for the unique processing mode of such a phenomenon
It is to improve centrifugal rotational speed, reduces centrifugation time, continues thereafter with and add appropriate n-hexane solvent）；Then supernatant is taken to add excessive
Ethanol is completely muddy up to solution, and solution now is centrifuged, takes precipitation to remove supernatant, is precipitated gained with n-hexane
Dissolved, add ethanol, acetone（The ratio of n-hexane, ethanol and acetone is 1:1:2）Carry out rush precipitation, the precipitation of gained
Dried 30 minutes under the conditions of 40 DEG C in vacuum dryer.
（3）This step carries out the preparation of main reaction, will（2）The CdZnS solid powders of middle gained are positioned in there-necked flask,
Add octadecylene（1-ODE）10ml and oleyl amine（OAm）4ml is heated to 80 DEG C and vacuumizes about 40 minutes, together（1）Described in,
Need to be evacuated weather repeatedly for three times before filling out argon gas, ensure to be completely disposed under ar gas environment in main reaction；Then fill then in argon
Reaction temperature is increased to 220 DEG C under compression ring border.
（4）This step is to prepare Cd presomas, and using CdO as Cd source, CdO is placed in 25ml there-necked flasks, then
Add a certain amount of oleic acid OA and octadecylene 1-ODE（V/V,1:1）, it is configured to determine the Cd presomas of concentration, then will reaction temperature
Degree is promoted to 250 DEG C, is then cooled to 100 DEG C of convenience and is subsequently added dropwise.
（5）When（3）When middle temperature reaches 220 DEG C, prepare injection Se and the cladding that Cd presomas carry out CdSe shells is added dropwise.
Specific implementation includes：The Se presomas that will be prepared first（Selenium powder+TBP tributylphosphine+1-ODE octadecylenes）Injection 20
Start that Cd presomas are added dropwise after minute, Se and Cd mol ratio are 1:The drop rate in 1, Cd source is maintained at the 2-3 seconds one and dripped, and is added dropwise
After timing sampling, in real time monitor quantum dot growth, that is, sample in n-hexane carry out absorption spectrum test, with anti-
Passage between seasonable, along with being grown into for quantum dot, there is corresponding Red Shift Phenomena in absorption spectrum, when continuous two sub-sampling
Absorption spectrum the cladding of next layer of CdSe shell can be carried out when not changing.Need exist for special attention in first layer
When CdSe shells coat, when Se presomas are initially injected, observation should be sampled, if there is green, then follow-up work
Work can suspend, because unnecessary Zn elements in CdZnS nuclear materials be present, form CdZnS/ZnSe, interrupt follow-up CdZnS/
CdSe synthesis.Purification processes are carried out after synthesis CdZnS/CdSe, specific method of purification includes：Stoste adds n-hexane and first
Alcohol（The two volume ratio is 1:2）Stirring extraction 2.5 minutes at 50 DEG C, then stratification, removes lower clear liquid, so extracts repeatedly
Take 4-5 times, the quantum dot after finally extracting adds acetone and promotees precipitation, and obtained precipitation is put into 40 DEG C of dryings in vacuum drying chamber
1h, grinding obtain powder.
（6）Above-mentioned steps（5）In synthesis can be adjusted flexibly, for different amounts of Se presomas and Cd presomas, meeting
Synthesize the CdZnS/CdSe quantum dots of each layer of different-thickness CdSe shell, so corresponding to be then different-waveband quantum dot,
Can according to device apply need adjust no ratio, obtain the luminescent spectrum of continuously adjustable.
2nd, the preparation scheme of LED light-emitting display devices includes：
（1）The glass substrate containing conducting film is cleaned first, glass simply gone with deionized water, cleaning agent successively
Dirt processing, then acetone, isopropanol are ultrasonically treated 20 minutes successively again, are finally placed in nitrogen gun drying standby in glove box.
（2）Hole injection layer is prepared, in glove box（O2<5ppm, H2O<5ppm）Under environment, glass substrate after cleaning
On with 3000 revs/min of rotating speed spin coating PEDOT:PSS, spin-coating time are that 25 points of fire is taken off in the subsequent 100 DEG C of nitrogen of 40 seconds
Clock, prepare PEDOT:PSS layers.
（3）Hole transmission layer is prepared, in PEDOT:With 2500 revs/min of rotating speed spin coating poly-TPD's on PSS layers
Chlorobenzene solution（Concentration is 8mg/ml）, spin-coating time be spin coatings in 40 seconds after the completion of in glove box（O2<5ppm, H2O<5ppm）In
Annealed under the conditions of 120 DEG C 20 minutes and form poly-TPD layers.
（4）Quantum dot light emitting layer is prepared, the above-mentioned CdZnS/CdSe quantum dots prepared are dissolved in normal octane, concentration
About 10mg/ml, rotating speed are 3000 revs/min, and spin-coating time is 50 seconds, in glove box（O2<5ppm, H2O<5ppm）In put
Put 10 minutes.
（5）Spin coating electron transfer layer on electron transfer layer, then quantum dot light emitting layer is prepared, rotating speed is 2500 revs/min, rotation
It is 50 seconds to apply the time, is then heated 20 minutes at 60 DEG C, forms electron transfer layer.
（6）Negative electrode is prepared, the device that spin coating is completed is put into vacuum evaporation cavity, evaporation cathode electrode aluminium, obtained complete
Light-emitting diode display part.
Claims (8)
1. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots, it is characterised in that method and step includes：
（1）Injection method is warmed by height first, then insulation synthesis CdZnS quantum dots；
（2）By the step（1）Obtained CdZnS quantum dots mix with corresponding ligand solvent is used as main reaction, then notes respectively
Enter, zwitterion is added dropwise is incubated to obtain CdZnS/CdSe nuclear shell structure quantum points.
2. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1, its feature
It is：The step（1）Middle Zn elements are excessive, and Zn and Cd mol ratio are 10:1.
3. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1, its feature
It is：The step（2）In be injected separately into, the order that is added dropwise zwitterion is first to inject anion, insulation 20 minutes and then
Cation is added dropwise.
4. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1, its feature
It is：The step（1）The CdZnS quantum dots of middle preparation need to be purified to obtain CdZnS powder, and purge process includes：Will
The CdZnS quantum dot stostes of the synthesis mix with n-hexane, multiple centrifuging and taking supernatant, remove unnecessary Zn elements, then
Supernatant is mixed with excess ethyl alcohol, centrifuged, and is dried in vacuo and obtains CdZnS quantum dot powder.
5. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1, its feature
It is：The step（1）The temperature of middle insulation is 310 DEG C, soaking time 10min.
6. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1, its feature
It is：The step（2）In the corresponding non-coordinating solvent that refers to be 1-ODE octadecylenes and oleyl amine.
7. a kind of preparation method of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1, its feature
It is：The step（2）The drop rate of cationic is one drop/2-3s, and holding temperature is 220 DEG C, and soaking time is
20min。
A kind of a kind of 8. LED hairs of preparation of anti-I type CdZnS/CdSe core/shell structure quantum dots according to claim 1
Light display device, it is characterised in that：Including set gradually ITO electro-conductive glass, hole injection layer, hole transmission layer, luminescent layer,
Electron transfer layer and electrode；Preparation method includes：By the method for spin coating by each layer successively spin-coating film, and each layer all exists
Dried under specified temp, electrode is then prepared by the method for evaporation again, be prepared into a complete LED light-emitting display device.
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| CN111234823A (en) * | 2020-03-11 | 2020-06-05 | 宁波东旭成新材料科技有限公司 | Synthesis method of quantum dots |
| CN112126434A (en) * | 2020-08-31 | 2020-12-25 | 济南大学 | AgInSe2Preparation method of-CdSe core-shell quantum dots |
| CN114672314A (en) * | 2020-12-24 | 2022-06-28 | Tcl科技集团股份有限公司 | Core-shell structure quantum dot, preparation method thereof, quantum dot light-emitting film and diode |
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| CN104910918A (en) * | 2015-04-30 | 2015-09-16 | 中国科学院半导体研究所 | Core-shell quantum dot material and preparation method thereof |
| CN105885848A (en) * | 2016-05-16 | 2016-08-24 | 南昌航空大学 | Preparation of Cd[x]Zn[1-x]S@ZnSe quantum dots and application of Cd[x]Zn[1-x]S@ZnSe quantum dots in solar cells |
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| CN104910918A (en) * | 2015-04-30 | 2015-09-16 | 中国科学院半导体研究所 | Core-shell quantum dot material and preparation method thereof |
| CN105885848A (en) * | 2016-05-16 | 2016-08-24 | 南昌航空大学 | Preparation of Cd[x]Zn[1-x]S@ZnSe quantum dots and application of Cd[x]Zn[1-x]S@ZnSe quantum dots in solar cells |
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| CN111234823A (en) * | 2020-03-11 | 2020-06-05 | 宁波东旭成新材料科技有限公司 | Synthesis method of quantum dots |
| CN112126434A (en) * | 2020-08-31 | 2020-12-25 | 济南大学 | AgInSe2Preparation method of-CdSe core-shell quantum dots |
| CN114672314A (en) * | 2020-12-24 | 2022-06-28 | Tcl科技集团股份有限公司 | Core-shell structure quantum dot, preparation method thereof, quantum dot light-emitting film and diode |
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