CN101191052B - Preparation method for CdSeS quantum dots nano particles - Google Patents
Preparation method for CdSeS quantum dots nano particles Download PDFInfo
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- 229910052711 selenium Inorganic materials 0.000 claims abstract description 18
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 6
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- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 3
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- UKUDSMQEWVNCOJ-UHFFFAOYSA-N 2,3,4,6-tetranitroaniline Chemical compound NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C([N+]([O-])=O)=C1[N+]([O-])=O UKUDSMQEWVNCOJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- ZQJAONQEOXOVNR-UHFFFAOYSA-N n,n-di(nonyl)nonan-1-amine Chemical compound CCCCCCCCCN(CCCCCCCCC)CCCCCCCCC ZQJAONQEOXOVNR-UHFFFAOYSA-N 0.000 claims description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical group CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 229910052786 argon Inorganic materials 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
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- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to a semiconductor CdSeS quantum dot nanoparticle with ternary components, which is novel and photoluminescence continuously adjustable with chemical compositions, and a preparation method thereof. Moore ratio of Cd: Se: S in the CdSeS quantum dot nanoparticle is 1: x: y; wherein, the x is more than or equal to 0.001 and less than or equal to 0.1, the y more than or equal to 0.1 less than or equal to 10.The CdSeS quantum dot nanoparticle in size range of 450-700nm has different photoluminescences and half-peak width is in range of 25-40nm. The preparation method of the CdSeS is that: inorganic compounds of cadmium, fatty acid and trialkyl amine of long chain are heated to 200 - 350 DEG C under protection of inert gas, so as to obtain solution A; then, trialkyl phosphine mixed solution of S, Se is added into the solution A; after reaction, mixture B of the CdSeS quantum dot nanoparticle and the long-chain trialkyl amine are made; at last, the CdSeS quantum dot nanoparticle is obtained by eliminating non-reaction matters, impurities and reaction solvent in the mixture B.
Description
Technical field
The present invention relates to a kind of novel quantum dot product, relate in particular to the CdSeS quantum dot nano-particle, and a kind of method for preparing the CdSeS quantum dot nano-particle.
Background technology
Quantum dot nano-particle can be described as accurate zero dimension semiconductor nanocrystal again.Because the nanoscale effect, electronics and hole are by quantum confinement, and less than Bohr's diameter the time, quantum dot nano-particle is become the discrete energy levels structure with molecular characterization by continuous energy level.Therefore after accepting energy (exciting), can launch the light of special wavelength.Why quantum dot nano-particle research is subjected to the attention of scientific circles and industrial community, particularly is subjected to the attention of biomedicine field, and reason is that its unique photoluminescent property has special application prospect in a lot of fields.
Compare with the traditional chemical fluorescence probe, the advantage that quantum dot nano-particle possesses comprises:
(1) quantum dot nano-particle of same chemical constitution, can launch the light of different colours according to different scale, be that its photoluminescence spectrum can be by the particle scale adjustment, therefore can be at visible light and even infrared spectral coverage " customization " needed quantum dot nano-particle as requested;
Therefore (2) excitation spectrum of quantum dot nano-particle is quite wide, overlaps each other, and selects single exciting light just can make the quantum dot nano-particle of different colours simultaneously luminous, collection when being fit to very much a plurality of echo signal;
(3) emission spectrum of quantum dot nano-particle is very narrow, can farthest avoid the overlapping of emission spectrum, improves the quality of image, also therefore can be used for light spectrum image-forming and visit agent;
(4) in comparable scope, the luminous intensity of quantum dot nano-particle is visited agent apparently higher than conventional fluorescent, and therefore the susceptibility that detects improves greatly;
(5) optical stability of quantum dot nano-particle is higher than traditional chemical spy agent far away, is fit to very much long-time the observation and dynamic studies;
(6) quantum dot nano-particle possesses big specific surface area, and the chemistry and the bio-modification of diversification can be provided, and selects suitable modification strategy, and quantum dot nano-particle can be avoided the toxic action to organism to greatest extent.
Therefore quantum dot nano-particle be a class to biological chemistry, molecular biology, cytobiology and medical research and the extremely important fluorescent probe of development, in life science, have huge application potential in the research.
The preparation of relevant quantum dot nano-particle becomes hot research in recent years.In organic system, prepared multiple IIB-VIB and IIIB-VB binary composition quantum dot at present, and based on this core-shell type quantum dot nano-particle, as CdSe and CdSe/ZnS quantum dot nano-particle.These quantum dot nano-particles all are to come tuning its emission wavelength by control particulate yardstick, but these quantum dot nano-particles all exist shortcoming or deficiencies such as preparation condition harshness, agents useful for same be inflammable and explosive.As (1) widely used Cd (Me) in synthetic
2, Zn (Et)
2Deng the chemical that is danger close, and cost is very high; (2) be not easy operation by particle scale control emission wavelength, and repeatability is bad, is unfavorable for mass preparation and application; (3) control the synthetic quantum dot nano-particle because the quantum dot nano-particle scale size of different colours is inconsistent by yardstick, to be subjected to a certain degree restriction being used for biomedical research, during as the motion of parallel study differing molecular, must consider the different problems of the limitation of movement degree that is caused by quantum dot yardstick difference.
Also has a kind of semiconductor-quantum-point glass in the prior art, as people such as Tian Qiang (" Beijing Normal University's journal ", 2001,37:205-207; 2003,39:636-639; People such as Jiang Desheng " optical technology ", 2005,30:30-32) mentioned CdSeS glass composite material.Be characterized in making the glass composite material with nonlinear optics speciality, this is different products with the quantum dot nano-particle that is used for biological medicine research.From state, this Quantum Dot Glass exists with block form, and the application's quantum dot nano-particle product exists with the pressed powder form, and can be dissolved in efficiently in the organic solution; From spectral quality, the photoluminescence spectrum peak width at half height of this Quantum Dot Glass is generally greater than 100nm, and has not only luminous spectrum peak, and the application's product peak width at half height has unique photoluminescence spectra generally between 25-40nm; From preparation process, this Quantum Dot Glass generally adopts scorification to make behind high temperature annealing, and the solution method that adopts with teachings herein is completely different.Therefore it doesn't matter for Quantum Dot Glass and the application's quantum dot nano-particle product.
From present development trend, quantum dot nano-particle research and range of application progressively enlarge, and particularly demonstrate good prospects for application at biomedicine field.Therefore develop favorable repeatability, can prepare in enormous quantities, optical property is stable, fluorescent property excellence, the continuously adjustable quantum dot nano-particle of spectrum seem very urgent.
Summary of the invention
The technical problem that the present invention will solve provides a kind of CdSeS quantum dot nano-particle, and the molar ratio of Cd: Se: S is 1 in this CdSeS quantum dot nano-particle: x: y, wherein 0.001≤x≤0.1,0.1≤y≤10; Along with the variation of x and y, this CdSeS quantum dot nano-particle has different photoluminescence spectrums in the 450-700nm scope, and peak width at half height is in the 25-40nm scope.
Another technical problem that the present invention will solve provides a kind of method of the CdSeS of preparation quantum dot nano-particle, and it may further comprise the steps:
(1) inorganic cadmic compound, lipid acid and long-chain trialkylamine are heated to 250-330 ℃ under the protection of rare gas element, obtain solution A;
(2) the trihydrocarbyl phosphine mixing solutions with S and Se is injected in the solution A that obtains in the step (1), and it is reacted, and obtains the mixture B of CdSeS quantum dot nano-particle and described long-chain trialkylamine;
(3) remove unreacted reactant, impurity and reaction solvent among the mixture B, obtain the CdSeS quantum dot nano-particle.
Preparation method of the present invention further comprises the vacuum drying step of quantum dot that will obtain in the step (3).
In step (1), be preferably based on the inorganic cadmic compound of 1mol, the consumption of lipid acid is 1-20mol, the consumption of long-chain trialkylamine is 1-60mol.
In step (2), based on the inorganic cadmic compound of 1mol, the consumption of Se is preferably 0.001-0.1mol; The consumption of S is preferably 0.1-10mol.In addition, in step (2), the temperature of solution A preferably remains on the steady temperature between 250-330 ℃.
In step (3), can use settling process to remove unreacted reactant, impurity and reaction solvent among the mixture B.
Preparation method of the present invention can regulate and control the quantum dot nano-particle photoluminescence spectrum by the relative proportion of each chemical element component in the control quantum dot nano-particle, make its photoluminescence spectrum adjustable continuously in the scope of 450-700nm, promptly can reach the purpose of carrying out spectral modulation at visible region.Preparation method of the present invention can carry out under mild conditions, repeats to prepare the quantum dot nano-particle with same emission wavelength in enormous quantities.
Because the quantum dot nano-particle nucleation process has great influence to the quantum dot nano-particle quality, and nucleation process is one and process rapidly, therefore is difficult to effectively control in synthetic; But the control chemical constitution is many easily more than control quantum dot nanoparticle growth in synthetic, therefore has remarkable advantages in the present invention aspect the repeatability preparation, also so as required the quantum dot nano-particle of " customization " required wavelength.As seen from the above analysis, product of the present invention is compared with existing quantum dot nano-particle, and tangible difference is all arranged from the chemical constitution to preparation method and on the photoluminescence spectra modulation strategy.
In addition, in the preparation of product of the present invention, all adopt reagent (seeing the summary of the invention part for details) commonly used,, do not have inflammable and explosive danger as CdO, Se, S and TOA etc., and with low cost; Preparation temperature generally at 250-330 ℃, finish by one kettle way, easy to operate, easily control.What is more important, the application of this type of reagent is to the not influence of quantum dot nano-particle optical property, its spectral quality excellence.Therefore, the invention provides the effective scheme of a kind of repeatability on a large scale preparation.
Among the present invention, key point is the accurate control and the material rate of temperature, and temperature has determined speed, the growth of quantum dot nano-particle nucleation, and the excellent summary of crystalline, and the chemical composition ratio is directly relevant with the quantum dot nano-particle photoluminescence spectrum.Therefore, stable temperature control is controlled the quality that has determined quantum dot nano-particle of the present invention with component.
The existing quantum dot nano-particle product of product of the present invention is compared, except that cost is lower, easy to operate, its comparable photoluminescence spectrum peak width at half height (closely related with size-grade distribution, the optical quality of quantum dot nano-particle) generally is stabilized in the 25-40nm scope, and the most common about 30nm.Its product is according to method and operation, and variation range is very big.
Embodiment
Further specify the present invention below in conjunction with concrete embodiment, but also limit scope of the present invention never in any form.
According to a first aspect of the invention, provide a kind of quantum dot nano-particle.More particularly, provide a kind of CdSeS quantum dot nano-particle, the molar ratio of Cd: Se: S is 1 in this CdSeS quantum dot nano-particle: x: y, wherein 0.001≤x≤0.1,0.1≤y≤10.Along with the variation of x and y, this CdSeS quantum dot nano-particle has different photoluminescence spectrums in the 450-700nm scope, and peak width at half height is in the 25-40nm scope.
In this CdSeS quantum dot nano-particle, preferred 0.003≤x≤0.08,0.2≤y≤6.
Preferred this CdSeS quantum dot nano-particle is along with the variation of x and y has different photoluminescence spectrums in the scope of 470-620nm.
The peak width at half height of the photoluminescence spectrum of preferred this CdSeS quantum dot nano-particle is less than 38nm.
A kind of method of the CdSeS of preparation quantum dot nano-particle is provided according to a second aspect of the invention.More particularly, this method may further comprise the steps:
(1) inorganic cadmic compound, lipid acid and long-chain trialkylamine are heated to 200-350 ℃ under the protection of rare gas element, obtain solution A;
(2) the trihydrocarbyl phosphine mixing solutions with S and Se is injected in the solution A that obtains in the step (1), and it is reacted, and obtains the mixture B of CdSeS quantum dot nano-particle and described long-chain trialkylamine;
(3) remove unreacted reactant, impurity and reaction solvent among the mixture B, obtain the CdSeS quantum dot nano-particle.
The method of the CdSeS of preparation quantum dot nano-particle of the present invention may further include the step (4) of the quantum dot that obtains in the vacuum drying step (3).
Below describe each step for preparing the method for CdSeS quantum dot nano-particle of the present invention in detail:
In step (1), inorganic cadmic compound is as the cadmium source of target CdSeS quantum dot nano-particle.Its kind is not specifically limited, but preferred cadmic compound, for example Cadmium oxide, cadmium stearate, Cadmium chloride fine powder, Cadmium Sulphate, cadmium carbonate and cadmium acetate etc.Wherein, preferred Cadmium oxide, Cadmium chloride fine powder and cadmium carbonate, more preferably Cadmium oxide.
In this step, lipid acid and long-chain trialkylamine serve as solvent and stablizer, and its kind is not specifically limited.From the angle that ensures that reaction is carried out, the boiling point of preferred employed lipid acid and trialkylamine is not less than 200 ℃, more preferably is not less than 250 ℃, most preferably is not less than 300 ℃.The example of the lipid acid that is fit to includes but not limited to saturated or undersaturated C
6-20Lipid acid, preferred C
10-18Lipid acid, more preferably TETRADECONIC ACID, palmitic acid, stearic acid and oleic acid, most preferably oleic acid.The example of the long-chain trialkylamine that is fit to includes but not limited to trihexylamine, trioctylamine and TNA trinonylamine etc., preferred trioctylamine.In addition, from the control reactant concn with promote inorganic cadmic compound dissolved angle, based on the inorganic cadmic compound of 1mol, the consumption of preferred fatty acid is 1-20mol, more preferably 1-15mol, further preferred 2-10mol; And based on the inorganic cadmic compound of 1mol, the consumption of preferred long-chain trialkylamine is 1-60mol, more preferably 5-50mol.
Any suitable rare gas element can be used as the rare gas element that uses in the step (1), includes but not limited to nitrogen, argon gas, helium or its arbitrary combination.Preferred rare gas element is nitrogen, argon gas or its combination.
In step (2), trihydrocarbyl phosphine serves as the solvent and the stablizer of reaction, and its kind is not particularly limited, and includes but not limited to trialkyl phosphine and triaryl phosphine.Preferred employed trihydrocarbyl phosphine is three C
4-8Alkylphosphines or three C
8-10Aryl phosphine, for example tributylphosphine, three hexyl phosphines, tri octyl phosphine and triphenylphosphine etc.; More preferably tri octyl phosphine or triphenylphosphine.As long as it can dissolve Se and S, the consumption of trihydrocarbyl phosphine is not particularly limited.
In this step, with respect to the inorganic cadmic compound of 1mol, the consumption of Se is preferably 0.001-0.1mol, more preferably 0.003-0.08mol; The consumption of S is preferably 0.1-10mol, more preferably 0.2-6mol.
In addition, in reaction process, the temperature of solution A preferably remains on the steady temperature between 200-350 ℃.If temperature of reaction is too high, other chemical reaction then takes place easily, thereby cause yield to reduce.If reaction temperature is spent low, be unfavorable for that then crystalline forms, thereby influence the quality of resulting CdSeS quantum dot nano-particle.
And the trihydrocarbyl phosphine mixing solutions of S and Se preferably was injected in 10 seconds in the solution A that obtains in the step (1), more preferably injected in 5 seconds, further preferably injected in 3 seconds.In addition, the reaction times of the trihydrocarbyl phosphine mixing solutions of solution A and S and Se was preferably 10 seconds-10 minutes.
In step (3), can use settling process to remove unreacted reactant, impurity and reaction solvent among the mixture B.Preferably the settling process in step (3) is following carries out: with the mixture B that obtains in the polar organic solvent precipitation step (2) 1-5 hour, and supernatant discarded; With the non-polar organic solvent dissolving, add the polar organic solvent sedimentation again, supernatant discarded then; This process repeated multiple times is until removing unreacted reactant, impurity and reaction solvent; Until the photoluminescence spectral pattern symmetry of resulting quantum dot nano-particle, single, not assorted peak.Polar organic solvent in this step can be methyl alcohol, ethanol or its mixture, and non-polar organic solvent can be chloroform, toluene, phosgene or its mixture.
Further set forth to various aspects of the present invention by the following examples.These embodiment provide for the purpose of description and interpretation, not should be understood to limit the spirit and scope of the present invention.
Embodiment
Embodiment 1
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under the protection of Ar gas, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 9.7mg, S powder 320mg, be dissolved among the 5ml TOP, make the mixing solutions of Se and S, be expelled in 3 seconds in the above-mentioned heating systems, reaction was carried out 10 seconds.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 535nm at last.
The peak width at half height of the photoluminescence spectrum of this quantum dot nano-particle QD-535nm is about 30nm.
Embodiment 2
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under the protection of Ar gas, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 11mg, S powder 6.4mg, be dissolved among the 5ml TOP, make the mixing solutions of Se and S, be expelled in 5 seconds in the above-mentioned heating systems, reaction was carried out 5 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 624nm at last.
The peak width at half height of the photoluminescence spectrum of this quantum dot nano-particle QD-624nm is about 40nm.
Embodiment 3
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under the protection of Ar gas, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 0.9mg, S powder 320mg is dissolved among the 5ml TOP, makes the mixing solutions of Se and S, in 10 seconds, be expelled in the above-mentioned heating systems, the reaction carried out 10 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 473nm at last.
The peak width at half height of the photoluminescence spectrogram of this quantum dot nano-particle QD-473nm is about 25nm.
Embodiment 4
With 344.8mg CdCO
3(2mmol), to place volume be the there-necked flask of 100ml for 2.5ml oleic acid and 20ml TOA, is heated to 300 ℃ under the Ar gas shiled, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 11mg, S powder 6.4mg is dissolved among the 5ml TOP, makes the mixing solutions of Se and S, in 5 seconds, be expelled in the above-mentioned heating systems, the reaction carried out 5 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 625nm, peak width at half height 37nm at last.
Embodiment 5
With 460.8mg CdAc
2(2mmol), to place volume be the there-necked flask of 100ml for 2.5ml oleic acid and 20ml TOA, is heated to 220 ℃ under the Ar gas shiled, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 11mg, S powder 6.4mg is dissolved among the 5ml TOP, makes the mixing solutions of Se and S, in 5 seconds, be expelled in the above-mentioned heating systems, the reaction carried out 5 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 620nm, peak width at half height 40nm at last.
Embodiment 6
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 330 ℃ under the Ar gas shiled, obtains colourless transparent solution.Take by weighing Se powder 11mg, S powder 6.4mg is dissolved among the 5ml TOP, makes the mixing solutions of Se and S, in 5 seconds, be expelled in the above-mentioned heating systems, the reaction carried out 5 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 622nm, peak width at half height 35nm at last.
Embodiment 7
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under the Ar gas shiled, obtains colourless transparent solution, is cooled to 200 ℃.Take by weighing Se powder 11mg, S powder 6.4mg is dissolved among the 5ml TOP, makes the mixing solutions of Se and S, in 5 seconds, be expelled in the above-mentioned heating systems, the reaction carried out 5 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is the CdSeS quantum dot nano-particle powder of 618nm, peak width at half height 39nm at last.
Embodiment 8
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under nitrogen protection, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 11mg, S powder 200mg is dissolved in the 5ml triphenylphosphine, heating for dissolving is made the mixing solutions (150 ℃) of Se and S, is expelled in 5 seconds in the above-mentioned heating systems, reaction was carried out 5 minutes.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is CdSeS quantum dot nano-particle powder, the peak width at half height 38nm of 627nm at last.
Embodiment 9
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under the protection of Ar gas, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 3.5mg, S powder 640mg, be dissolved among the 5ml TOP, make the mixing solutions of Se and S, be expelled in 3 seconds in the above-mentioned heating systems, reaction was carried out 10 seconds.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is CdSeS quantum dot nano-particle powder, the peak width at half height 37nm of 503nm at last.
Embodiment 10
It is the there-necked flask of 100ml that 256.8mg CdO (2mmol), 2.5ml oleic acid and 20ml TOA are placed volume, is heated to 300 ℃ under the protection of Ar gas, and keeps stable, obtains colourless transparent solution.Take by weighing Se powder 7.4mg, S powder 480mg, be dissolved among the 5ml TOP, make the mixing solutions of Se and S, be expelled in 5 seconds in the above-mentioned heating systems, reaction was carried out 10 seconds.The quantum dot nano-particle that obtains is used ethanol sedimentation 2 hours, and supernatant discarded with the minimum of chloroform dissolving, adds the ethanol sedimentation again, and is centrifugal, supernatant discarded.With quantum dot nano-particle vacuum-drying, get final product to such an extent that emission wavelength is CdSeS quantum dot nano-particle powder, the peak width at half height 40nm of 526nm at last.
Can under the situation of principle that does not depart from claim of the present invention and defined and scope, product of the present invention and method be made amendment.
Claims (16)
1. CdSeS quantum dot nano-particle, the molar ratio that it is characterized in that Cd: Se: S in the described CdSeS quantum dot nano-particle is 1: x: y, 0.001≤x≤0.1 wherein, 0.1≤y≤10, and wherein along with the variation of x and y, described CdSeS quantum dot nano-particle has different photoluminescence spectrums in the scope of 450-700nm, and peak width at half height is in the scope of 25-40nm.
2. CdSeS quantum dot nano-particle according to claim 1 is characterized in that the variation along with x and y, and described CdSeS quantum dot nano-particle has different photoluminescence spectrums in the scope of 470-620nm.
3. CdSeS quantum dot nano-particle according to claim 1, the photoluminescence spectrum peak width at half height that it is characterized in that described CdSeS quantum dot nano-particle is less than 38nm.
4. CdSeS quantum dot nano-particle according to claim 1 is characterized in that wherein 0.003≤x≤0.08,0.2≤y≤6.
5. method for preparing the CdSeS quantum dot nano-particle is characterized in that may further comprise the steps:
(1) inorganic cadmic compound, lipid acid and long-chain trialkylamine are heated to 200-350 ℃ under the protection of rare gas element, obtain solution A;
(2) the trihydrocarbyl phosphine mixing solutions with S, Se is injected in the solution A that obtains in the step (1), it is reacted, obtain the mixture B of CdSeS quantum dot nano-particle and described long-chain trialkylamine, wherein, inorganic cadmic compound based on 1mol, the consumption of Se is 0.001-0.1mol, and the consumption of S is 0.1-10mol;
(3) remove unreacted reactant, impurity and reaction solvent, obtain the CdSeS quantum dot nano-particle.
6. method according to claim 5 is characterized in that further comprising step (4): with the quantum dot vacuum-drying that obtains in the step (3).
7. method according to claim 5 is characterized in that in the step (1), described inorganic cadmic compound is Cadmium oxide, Cadmium chloride fine powder or cadmium carbonate.
8. method according to claim 5 is characterized in that in step (1) based on the described inorganic cadmic compound of 1mol, the consumption of described lipid acid is 1-20mol, and the consumption of described long-chain trialkylamine is 1-60mol.
9. method according to claim 5 is characterized in that in the step (1), described lipid acid is TETRADECONIC ACID, palmitic acid, stearic acid or oleic acid.
10. method according to claim 5 is characterized in that in the step (1), described long-chain trialkylamine is trihexylamine, trioctylamine or TNA trinonylamine.
11. method according to claim 5 is characterized in that in step (2) based on the inorganic cadmic compound of 1mol, the consumption of Se is 0.003-0.08mol, the consumption of S is 0.2-6mol.
12. method according to claim 5 is characterized in that described solution A remains on the steady temperature between 200-350 ℃ in step (2).
13., it is characterized in that the trihydrocarbyl phosphine described in the step (2) is tri octyl phosphine or triphenylphosphine according to the method described in the claim 5.
14. method according to claim 5 is characterized in that removing unreacted reactant, impurity and reaction solvent with settling process in step (3).
15. method according to claim 14, it is characterized in that the settling process described in the step (3) is following carries out: with mixture B1～5 that obtain in the polar organic solvent precipitation step (2) hour, and supernatant discarded; With the non-polar organic solvent dissolving, add the polar organic solvent sedimentation again, supernatant discarded then; This process repeated multiple times is until removing unreacted reactant, impurity and reaction solvent; Until the photoluminescence spectral pattern symmetry of resulting quantum dot nano-particle, single, not assorted peak.
16. method according to claim 15 is characterized in that described polar organic solvent is ethanol, methyl alcohol or its mixture, described non-polar organic solvent is chloroform, toluene, phosgene or its mixture.
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| CN102344811B (en) * | 2011-07-26 | 2014-01-15 | 合肥工业大学 | Method for preparing ternary alloy quantum dots in ole-morpholine solvent |
| CN102585807B (en) * | 2012-01-16 | 2014-03-26 | 中国科学院长春应用化学研究所 | Quantum dot with adjustable emission spectrums and preparation method thereof |
| CN103484123A (en) * | 2013-09-22 | 2014-01-01 | 天津晟宝量子点制造有限公司 | Novel preparation method for ternary alloy type CdSeS quantum dots |
| 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 |
| CN106318372B (en) * | 2015-09-15 | 2019-09-27 | 中国科学院遗传与发育生物学研究所 | A kind of fluorescent nano particle and its synthetic method, application |
| JP7043727B2 (en) * | 2017-01-31 | 2022-03-30 | 大日本印刷株式会社 | Deterioration evaluation method of optical wavelength conversion sheet, optical wavelength conversion sheet, backlight device, and image display device |
| CN109046453B (en) * | 2018-07-03 | 2020-11-20 | 山东交通学院 | Preparation method and application of CdSeS point complex composite material |
| WO2020048527A1 (en) * | 2018-09-07 | 2020-03-12 | Tcl集团股份有限公司 | Composite material and quantum dot light emitting diode |
| CN111378451A (en) * | 2018-12-29 | 2020-07-07 | Tcl集团股份有限公司 | Preparation method of quantum dots |
| CN113528140B (en) * | 2021-08-25 | 2023-04-18 | 合肥福纳科技有限公司 | Method for removing impurity peaks in quantum dot emission spectrum |
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