CN105505393A - Method for rapidly and remarkably enhancing fluorescence intensity of quantum dots - Google Patents

Method for rapidly and remarkably enhancing fluorescence intensity of quantum dots Download PDF

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Publication number
CN105505393A
CN105505393A CN201510968928.3A CN201510968928A CN105505393A CN 105505393 A CN105505393 A CN 105505393A CN 201510968928 A CN201510968928 A CN 201510968928A CN 105505393 A CN105505393 A CN 105505393A
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cdse
quantum dot
fluorescence intensity
quantum dots
cdscore
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CN201510968928.3A
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董安钢
刘丽敏
杨东
胡建华
吕龙飞
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Fudan University
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Fudan University
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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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Abstract

The invention belongs to the technical field of inorganic nanometer materials, and particularly relates to a method for rapidly and remarkably enhancing the fluorescence intensity of the CdSe quantum dots. The method includes the steps of firstly, preparing the CdSe quantum dots under the condition of high-temperature N2 through a method disclosed in the prior art; secondly, processing the CdSe quantum dots through a formamide solution of ammonium sulfide or potassium sulphide at the room temperature, and generating CdSe/CdScore-shell semiconductor nanometer particles; thirdly, adding oleylamine and trioctylphosphine (TOP for short) to passivate the surfaces of the CdSe/CdScore-shell semiconductor nanometer particles, and remarkably increasing yield of the quanta within a short period of time. The method is simple, gentle in reaction condition and capable of rapidly and remarkably enhancing the fluorescence intensity of the CdSe quantum dots. The semiconductor quantum dots which are prepared through the method and high in quantum yield have wide application prospects in the fields of photodiodes, fluorescent markers and the like.

Description

A kind of method significantly strengthening quantum dot fluorescence intensity fast
Technical field
The invention belongs to technical field of inorganic nanometer material, be specifically related to a kind of method significantly strengthening quantum dot fluorescence intensity fast.
Background technology
The optical characteristics of CdSe/CdScore-shell nano-quantum point is closely related with particle diameter and pattern, so the characteristic of the optics that can be regulated by the size and pattern regulating nanometer particle size, this also just makes the aspects such as its scene effect transistor, solar cell, photodetector have a wide range of applications.And the chemical structure of the type I of its uniqueness, make electronics and hole concentrate in core, make it show more excellent fluorescent characteristic, make it be widely used in fluorescent mark, LED etc.
Tradition preparation CdSe/CdScore-shell nanoparticle is under the high temperature conditions, is added to by the precursor solution of Cd and S in the organic phase solution of CdSe core, makes it at the shell of surface growth one deck CdS of core.
The present invention is at ambient temperature by the homogeneous CdSe quantum dot of the formamide soln process traditional method synthesis of ammonium sulfide or potassium sulphide, produces CdSe/CdScore-shell semi-conductor nano particles.Then add oleyl amine and TOP makes the surface passivation of CdSe/CdScore-shell semi-conductor nano particles, improve the quantum yield of CdSe semiconductor-quantum-point fast significantly.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate method significantly strengthening quantum dot fluorescence intensity fast.
The method of quick enhancing quantum dot fluorescence intensity provided by the invention, concrete steps are as follows:
(1) under normal temperature, with ammonium sulfide or the formamide soln process different-grain diameter of potassium sulphide or the CdSe nanoparticle 5-10 minute of different-shape, S 2-replacing to fall organic Long carbon chain part of CdSe nanoparticle surface, semi-conductor nano particles is made to exchange to polar solvent, meanwhile, S 2-also with the Se on surface 2-generation negatively charged ion replaces, and produces CdSe/CdScore-shell semi-conductor nano particles;
(2) S of CdSe/CdScore-shell semi-conductor nano particles is exchanged with oleyl amine 2-part, makes quantum dot exchange to normal hexane phase;
(3) trioctylphosphine phosphorus (be called for short TOP) is joined above-mentioned normal hexane mutually in, leave standstill 30-60 minute.
Quantum dot fluorescence through above-mentioned process obviously strengthens.
In the present invention, CdSe nanoparticle by method disclosed in prior art at high temperature N 2prepare under condition.
In step of the present invention (1), the formamide soln concentration of ammonium sulfide is 10-50 μ L/mL, and the formamide soln concentration of potassium sulphide is 5-25mg/mL.
In step of the present invention (2), oleyl amine: CdSe(mol ratio) be 40:1 ~ 80:1.
In step of the present invention (3), TOP:CdSe(mol ratio) be 30:1 ~ 60:1.
In the present invention, described CdSe quantum dot can have different-shape (as nano particle or nanometer rod) and different size (2.1nm to 7.7nm).
In the present invention, sulphur compound process CdSe quantum dot is used to realize S 2-with Se 2-negatively charged ion replace; With oleyl amine and TOP passivation quantum dot.Through twice ligand exchange, quantum dot is first exchanged to polar solvent and exchange to again non-polar solvent phase mutually.
The inventive method is simple, reaction conditions is gentle, significantly can strengthen the fluorescence intensity of CdSe quantum dot fast.The semiconductor-quantum-point of the high quantum production rate that the present invention obtains, has extensively wide application prospect in the field such as photorectifier, fluorescent mark.
Accompanying drawing explanation
Fig. 1 is the schematic diagram (daylight and UV-irradiation under) of each step of Fluorescence Increasing.
Fig. 2 is ultraviolet (a) and the fluorogram (b) that 4.3nmCdSe nano-particle fluorescence strengthens front and back.
Fig. 3 is the TEM figure before and after the process of 4.3nmCdSe nano particle.A () is before process, after (b) process.
Fig. 4 is power spectrum change before and after 4.3nmCdSe nano-particle fluorescence enhancement process.A () is before process, after (b) process.
Embodiment
Below by enforcement case row, the present invention will be further elaborated.Quantum dot used in the present invention can synthesize by method disclosed in prior art.
Embodiment 1:
1.1. oil phase method synthesis 4.3nmCdSe nano particle is adopted
4.3nmCdSe nano particle synthesizes.Se precursor solution is made by the 2.8mLTOP of 316mgSe powder.256mgCdO, 3.5mL oleyl amine and 40mL 18 is rare is heated to 220 DEG C, keeps 220 DEG C to be achromaticity and clarification to solution.Then solution cools to 120 DEG C, vacuumizes 1h.At N 2under condition, add oleyl amine 7mL.Be heated to 260 DEG C, Se precursor solution 0.6ml is injected in the precursor solution of Cd.React 10 minutes.In ensuing 30 minutes, remaining Se precursor solution is dropwise added.Cooling, uses washing with alcohol several times, is finally dissolved in hexane solution.
1.2.S 2-surface treatment quantum point particle
1.2.1. (NH 4) 2the surface treatment of S.Under normal temperature, with (the NH of 10 μ L/mL 4) 2s (aqueous solution of 40%-48%) formamide soln (1mL) processes 0.01MCdSe quantum dot (5mL), S 2-replace to fall organic Long carbon chain part of CdSe nanoparticle surface, make semi-conductor nano particles exchange in methane amide, vigorous stirring 10 minutes.
1.2.2.K 2the surface treatment of S.Under normal temperature, use 5mg/mLK 2s formamide soln (1.5mL) processes 0.01MCdSe quantum dot (5mL), S 2-replace to fall organic Long carbon chain part of CdSe nanoparticle surface, make semi-conductor nano particles exchange in methane amide, vigorous stirring 10 minutes.
1.3. with oleyl amine, quantum dot is exchanged to organic phase
1mL oleyl amine and 5mL hexane solution will be entered in the formamide soln of above-mentioned quantum dot, vigorous stirring, make oleyl amine exchange the S on surface 2-part, quantum dot exchanges to normal hexane phase from formyl amine layer.
1.4. add TOP and strengthen fluorescence
Add 1mLTOP, stir, leave standstill 30 minutes.
Embodiment 2:
1.1. oil phase method synthesis CdSe nanometer rod is adopted
CdSe nanometer rod is synthesized.By 31mgSe powder, 723mgTOP, 95mgTBP(tributyl phosphorus), 150mg toluene heats 150 DEG C to dissolving completely, makes Se precursor solution.105mgCdO, 449mgTDPA(tetradecyl phosphoric acid) and 1.13gTOPO (trioctylphosphine oxide) be heated to 100 DEG C, vacuumize 30 minutes.N 2being heated to 300 DEG C under condition to solution is achromaticity and clarification.Be down to normal temperature, N 2lower aging 1 day.Cd source is heated to 320 DEG C, adds the precursor solution of Se, be cooled to 250 DEG C, reaction 1h.Cooling, uses washing with alcohol several times, is finally dissolved in hexane solution.
1.2.S 2-surface treatment CdSe nanometer rod
1.2.1. (NH 4) 2the surface treatment of S.Under normal temperature, with (the NH of 10 μ L/mL 4) 2s (aqueous solution of 40%-48%) formamide soln (1mL) processes 0.01MCdSe nanometer rod solution (5mL), vigorous stirring 10 minutes, S 2-replace to fall organic Long carbon chain part of CdSe nanoparticle surface, CdSe nanometer rod is exchanged in methane amide.
1.2.2.K 2the surface treatment of S.Under normal temperature, use 5mg/mLK 2s formamide soln (1.5mL) processes 0.01MCdSe nanometer rod (5mL), S 2-replace to fall organic Long carbon chain part of CdSe nanoparticle surface, make CdSe nanometer rod exchange in methane amide, vigorous stirring 10 minutes.
1.3. with oleyl amine, CdSe nanometer rod is exchanged to organic phase
1mL oleyl amine and 5mL hexane solution will be entered in the formamide soln of quantum dot, vigorous stirring, make oleyl amine exchange the S on surface 2-part, CdSe nanometer rod exchanges to normal hexane phase from formyl amine layer.
1.4. add TOP and strengthen fluorescence
Add 1mLTOP, stir, leave standstill 30 minutes.
Below with 4.3nmCdSe semiconductor nanoparticle for representative, analyzed by UV, visible light (UV-Vis), fluorescence (PL), TEM, X-ray energy spectrum, quantum yield (QY).
1. the schematic diagram (daylight and UV-irradiation under) of each step of Fluorescence Increasing
Fig. 1 is the photo of each step of 4.3nmCdSe semiconductor nanoparticle Fluorescence Increasing process respectively under daylight and UV-irradiation.Before and after process, the comparison of photo, can find out that fluorescence is significantly improved.
2. optical analysis (UV-Vis and PL)
Fig. 2 is UV-Vis and the PL spectrogram before and after 4.3nmCdSe semiconductor nanoparticle Fluorescence Increasing, can find out, before and after process, fluorescence significantly improves.
3.TEM analyzes
Fig. 3 is the TEM contrast before and after 4.3nmCdSe semiconductor nanoparticle Fluorescence Increasing.Can find out, after process, the pattern of particle still can keep.
4. energy spectrum analysis
Fig. 4 is power spectrum change before and after 4.3nmCdSe semiconductor nanoparticle Fluorescence Increasing, can find out that the content of Se reduces, and the content of S is from increasing to some extent.That is, CdSe/CdScore-shell structure is defined in treating processes.
Table 1 is 2.1nm, 3.1nm, 4.4nm, 7.7nmCdSe nano particle and the fluorescence quantum yield of CdSe nanometer rod before and after Fluorescence Increasing process (QY).
Table 1
。

Claims (5)

1. significantly strengthen a method for quantum dot fluorescence intensity fast, it is characterized in that concrete steps are as follows:
(1) under normal temperature, with ammonium sulfide or the formamide soln process different-grain diameter of potassium sulphide or the CdSe nanoparticle 5-10 minute of different-shape, S 2-replacing to fall organic Long carbon chain part of CdSe nanoparticle surface, semi-conductor nano particles is made to exchange to polar solvent, meanwhile, S 2-also with the Se on surface 2-generation negatively charged ion replaces, and produces CdSe/CdScore-shell semi-conductor nano particles;
(2) S of CdSe/CdScore-shell semi-conductor nano particles is exchanged with oleyl amine 2-part, makes quantum dot exchange to normal hexane phase;
(3) TOP is joined above-mentioned normal hexane mutually in, leave standstill 30-60 minute.
2. the method significantly strengthening quantum dot fluorescence intensity fast according to claim 1, it is characterized in that in step (1), the formamide soln concentration of ammonium sulfide is 10-50 μ L/mL, and the formamide soln concentration of potassium sulphide is 5-25mg/mL.
3. the method significantly strengthening quantum dot fluorescence intensity fast according to claim 1, it is characterized in that in step (2), the mol ratio of oleyl amine and CdSe is 40:1 ~ 80:1.
4. the method significantly strengthening quantum dot fluorescence intensity fast according to claim 1, it is characterized in that in step (3), the mol ratio of TOP and CdSe is 30:1 ~ 60:1.
5. the method significantly strengthening quantum dot fluorescence intensity fast according to claim 1, is characterized in that described CdSe quantum dot is nano particle or nanometer rod, is of a size of 2.1nm to 7.7nm.
CN201510968928.3A 2015-12-22 2015-12-22 Method for rapidly and remarkably enhancing fluorescence intensity of quantum dots Pending CN105505393A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860969A (en) * 2016-05-13 2016-08-17 天津大学 Method for improving fluorescence performance of carbon quantum dots
CN109988552A (en) * 2017-12-29 2019-07-09 Tcl集团股份有限公司 Quantum dot film and preparation method thereof and QLED device
WO2020073927A1 (en) * 2018-10-09 2020-04-16 Tcl集团股份有限公司 Method for preparing nano crystal having core-shell structure

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Publication number Priority date Publication date Assignee Title
CN103361066A (en) * 2013-06-28 2013-10-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step
CN104327856A (en) * 2014-08-13 2015-02-04 南方科技大学 Method for preparing high-quantum-yield narrow-half-peak-width nuclear-shell quantum dot through TOP-assisted SILAR technology
CN105154086A (en) * 2015-09-29 2015-12-16 复旦大学 Method for preparing CdSe/CdS nuclear shell semiconductor quantum dots at normal temperature

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN103361066A (en) * 2013-06-28 2013-10-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step
CN104327856A (en) * 2014-08-13 2015-02-04 南方科技大学 Method for preparing high-quantum-yield narrow-half-peak-width nuclear-shell quantum dot through TOP-assisted SILAR technology
CN105154086A (en) * 2015-09-29 2015-12-16 复旦大学 Method for preparing CdSe/CdS nuclear shell semiconductor quantum dots at normal temperature

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Title
CHIH-JUNG CHEN，ET AL.: "Thiol treatment to enhance photoluminescence and electroluminescence of CdSe/CdS core–shell quantum dots prepared by thermal cycling of single source precursors", 《RSC ADVANCES》 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860969A (en) * 2016-05-13 2016-08-17 天津大学 Method for improving fluorescence performance of carbon quantum dots
CN109988552A (en) * 2017-12-29 2019-07-09 Tcl集团股份有限公司 Quantum dot film and preparation method thereof and QLED device
WO2020073927A1 (en) * 2018-10-09 2020-04-16 Tcl集团股份有限公司 Method for preparing nano crystal having core-shell structure

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Application publication date: 20160420