CN105038798A - Method for preparing cadmium selenide quantum dot - Google Patents
Method for preparing cadmium selenide quantum dot Download PDFInfo
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- CN105038798A CN105038798A CN201510518400.6A CN201510518400A CN105038798A CN 105038798 A CN105038798 A CN 105038798A CN 201510518400 A CN201510518400 A CN 201510518400A CN 105038798 A CN105038798 A CN 105038798A
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Abstract
The invention relates to a method for preparing a cadmium selenide quantum dot. The method comprises: providing a cadmium precursor solution, wherein the cadmium precursor solution comprises cadmium oxide, long-chain aliphatic amine and short-chain aliphatic amine; providing a selenium precursor solution, wherein the selenium precursor solution comprises selenium powder, long-chain aliphatic amine and short-chain aliphatic amine; mixing the cadmium precursor solution and selenium precursor solution to obtain a precursor solution mixture; heating the precursor solution mixture to obtain a quantum dot solution, wherein the quantum dot solution contains cadmium selenide quantum dots. The nucleation and growth are synergistically controlled by utilizing the mixed aliphatic amine, which improves the monodispersity of the quantum dot; moreover, continuity in production can be realized, and the industrialized production of the quantum dot can be facilitated.
Description
Technical field
The present invention relates to chemical field, particularly, relate to the method preparing CdSe quantum dots.
Background technology
Compared to traditional organic fluorescence materials, quantum dot is easily excited, and sends one-color fluorescence, and not easily by photobleaching.Therefore, quantum dot has potential using value widely in a lot of field such as solar cell, photodiode, medical treatment.Wherein, the II-VI group quantum dots such as CdSe, CdS, CdTe can cover whole visible spectrum due to its emitting fluorescence wavelength, and receive much concern.
Conventional synthesis CdSe quantum dot utilizes organic hot solvent one kettle way, due to one kettle way process have temperature heterogeneity, cannot the factor such as continuous seepage, device amplifies difficulty, causes that quantum dot production cost is higher and monodispersity is bad.And because heat and mass transfer performance is remarkable, controllability is strong in microchannel, for continuous seepage high-quality CdSe quantum dot is provided convenience.In existing method, no matter be one kettle way or microchannel synthetic method, synthesis CdSe quantum dot completes crystal nucleation and process of growth often under identical conditions, and this just causes the monodispersity of CdSe quantum dot not high, and fluorescence spectrum peak width at half height is at more than 40nm.
Thus, the method preparing CdSe quantum dots haves much room for improvement.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.For this reason, one object of the present invention be to propose a kind of have product monodispersity good, can the CdSe quantum dots novel method prepared of serialization, wherein, this CdSe quantum dots is nanocrystalline.
According to an aspect of the present invention, the invention provides a kind of method preparing CdSe quantum dots.According to embodiments of the invention, the method comprises: provide cadmium precursor aqueous solution, and wherein, described cadmium precursor aqueous solution comprises Cadmium oxide, long-chain fat amine and short-chain fat amine; There is provided selenium precursor aqueous solution, wherein, described selenium precursor aqueous solution comprises selenium powder, long-chain fat amine and short-chain fat amine; Described cadmium precursor aqueous solution and described selenium precursor aqueous solution are carried out combination treatment, to obtain precursor aqueous solution mixture; Described precursor aqueous solution mixture is carried out heat treated, to obtain quantum dot solution, containing described CdSe quantum dots in described quantum dot solution.
Contriver is surprised to find, method of the present invention is utilized to prepare CdSe quantum dots, have simple to operate, easy to make, regulate and control the advantages such as accurate, and, the present invention utilizes mixing-in fat amine coordinated regulation nucleation and growth, contribute to improving the monodispersity of quantum dot, and can continuous seepage, be conducive to the suitability for industrialized production of quantum dot.
In addition, the method preparing CdSe quantum dots according to the above embodiment of the present invention, can also have following additional technical characteristic:
According to embodiments of the invention, the mol ratio of described Cadmium oxide, described long-chain fat amine and described short-chain fat amine is 1:(50-70): (50-70) preferably, is 1:60:60.
According to embodiments of the invention, the mol ratio of described selenium powder, described long-chain fat amine and described short-chain fat amine is 1:(2-5): (2-5) preferably, is 1:3:3.
According to embodiments of the invention, described short-chain fat amine is at least one being selected from octylame, ten amine and amino dodecane.
According to embodiments of the invention, described long-chain fat amine is at least one being selected from tetradecy lamine, cetylamine, stearylamine and oleyl amine.
According to embodiments of the invention, described cadmium precursor aqueous solution is obtained by following steps: Cadmium oxide, long-chain fat amine and short-chain fat amine are mixed, obtain the first mixture; Described first mixture is mixed with oleic acid and trioctylphosphine, utilizes 1-octadecylene to dissolve, to obtain the first mixed solution; Described first mixed solution is carried out heat treated, to obtain cadmium precursor aqueous solution.
According to embodiments of the invention, described selenium precursor aqueous solution is obtained by following steps: selenium powder, long-chain fat amine and short-chain fat amine are mixed, obtain the second mixture; Described second mixture is mixed with tri-n-octyl phosphine, utilizes 1-octadecylene to dissolve, to obtain the second mixed solution; Described second mixed solution is carried out heat treated, to obtain selenium precursor aqueous solution.
According to embodiments of the invention, sampler is utilized to provide described selenium precursor aqueous solution and described cadmium precursor aqueous solution respectively,
According to embodiments of the invention, described sampler provides described cadmium precursor aqueous solution and described selenium precursor aqueous solution with the speed of 50 μ L/min.
According to embodiments of the invention, described heat treated utilizes oil bath under the condition of 210-280 degree Celsius, and heating 30-50 carries out, preferably, under the condition of 260-280 degree Celsius second.
According to embodiments of the invention, the method comprises further: by described quantum dot solution and the first precipitant mix, to obtain the first precipitation; By described first precipitation be dissolved in organic solvent, and with the second precipitant mix, to obtain the second precipitation; And described second precipitation is dried grinding, to obtain powder of cadmium selenide quanta dots capable.
According to embodiments of the invention, described first precipitation agent is dehydrated alcohol, and described second precipitation agent is acetone.
Additional aspect of the present invention and advantage will part provide in the following description, and part will become obvious from the following description, or be recognized by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage will become obvious and easy understand from accompanying drawing below combining to the description of embodiment, wherein:
Fig. 1 shows the schema preparing CdSe quantum dots according to an embodiment of the invention;
Fig. 2 shows the structural representation of microscale reactor according to an embodiment of the invention;
Fig. 3 shows the collection of illustrative plates picture of CdSe quantum dots uv-visible absorption spectra first excitation peak peak value according to an embodiment of the invention;
Fig. 4 shows the collection of illustrative plates picture of CdSe quantum dots fluorescence emission spectrum half-value width according to an embodiment of the invention;
Fig. 5 shows the collection of illustrative plates picture of CdSe quantum dots uv-visible absorption spectra according to an embodiment of the invention;
Fig. 6 shows CdSe quantum dots TEM photo according to an embodiment of the invention.
Embodiment
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Being exemplary below by the embodiment be described with reference to the drawings, only for explaining the present invention, and can not limitation of the present invention being interpreted as.
In describing the invention, term " longitudinal direction ", " transverse direction ", " on ", D score, "front", "rear", "left", "right", " vertically ", " level ", " top ", the orientation of the instruction such as " end " or position relationship be based on orientation shown in the drawings or position relationship, be only the present invention for convenience of description instead of require that the present invention with specific azimuth configuration and operation, therefore must can not be interpreted as limitation of the present invention.
It should be noted that, term " first ", " second " only for describing object, and can not be interpreted as instruction or hint relative importance or imply the quantity indicating indicated technical characteristic.Thus, be limited with " first ", the feature of " second " can express or impliedly comprise one or more these features.Further, in describing the invention, except as otherwise noted, the implication of " multiple " is two or more.
According to an aspect of the present invention, the invention provides a kind of method preparing CdSe quantum dots.With reference to figure 1, according to embodiments of the invention, the method is explained.According to embodiments of the invention, the method comprises:
S100: cadmium precursor aqueous solution is provided
According to embodiments of the invention, this cadmium precursor aqueous solution comprises Cadmium oxide, long-chain fat amine and short-chain fat amine.Thus, it should be noted that, adopt long-chain fat amine and short-chain fat amine to prepare cadmium precursor aqueous solution as part, on the one hand, the amido electron rich on aliphatic amide, to can be used for electronics to the Cd of electron deficiency, produces weak coordination; On the other hand, because the sterically hindered of short-chain fat amine is less than long-chain fat amine, short-chain fat amine is when temperature is lower than its boiling point, understand preferential and Cd coordination, temperature of reaction close to and boiling point higher than short-chain fat amine time, the mating reaction of short-chain fat amine and Cd is opened, long-chain fat amine can with Cd coordination.In crystal nucleation process of growth, the simple nucleation and growth speed controlled by short-chain fat amine is all higher than the speed controlled by long-chain fat amine merely, but nucleation process requires blast nucleation, namely The faster the better for nucleation rate, process of growth requires stable growth, and the too fast speed of growth can affect the monodispersity of CdSe quantum dot crystal.In whole reaction process, temperature is increased to temperature of reaction fast from room temperature, if final temperature of reaction is higher than the boiling point of short-chain fat amine, so in whole temperature-rise period, short-chain fat amine and long-chain fat amine can alternately with Cd coordination, start the blast nucleation that short-chain fat amine coordination regulation and control contribute to crystal, long-chain fat amine coordination afterwards contributes to the stable growth of crystal, and the CdSe crystal monodispersity of gained is better.
According to some embodiments of the present invention, the mol ratio of Cadmium oxide, long-chain fat amine and short-chain fat amine is 1:(50-70): (50-70).Thus, in this quality than under scope, Cadmium oxide is easier to be combined with long-chain fat amine and short-chain fat amine, and the synergy of long-chain fat amine and short-chain fat amine well, contributes to the stably growth of crystal, obtains CdSe crystal monodispersity good.According to preferred embodiments more of the present invention, the mol ratio of Cadmium oxide, long-chain fat amine and short-chain fat amine is 1:60:60.In this quality than under scope, Cadmium oxide is easier to be combined with long-chain fat amine and short-chain fat amine, and the synergy of long-chain fat amine and short-chain fat amine is better, contributes to more stably growing of crystal, obtains CdSe crystal monodispersity better.
According to embodiments of the invention, short-chain fat amine is at least one being selected from octylame, ten amine and amino dodecane.Thus, this kind of short-chain fat amine is easy to Cadmium oxide and selenium powder combines, and coordination regulating effect is good, contributes to the explosive nucleation of crystal.
According to embodiments of the invention, long-chain fat amine is at least one being selected from tetradecy lamine, cetylamine, stearylamine and oleyl amine.Thus, this kind of long-chain fat amine is easy to Cadmium oxide and selenium powder combines, and coordination regulating effect is good, contributes to the stable growth of crystal.
According to some embodiments of the present invention, cadmium precursor aqueous solution is obtained by following steps: Cadmium oxide, long-chain fat amine and short-chain fat amine are mixed, obtain the first mixture; This first mixture is mixed with oleic acid and trioctylphosphine, utilizes 1-octadecylene to dissolve, obtain the first mixed solution; This first mixed solution is carried out heat treated, obtains cadmium precursor aqueous solution.Thus, the cadmium precursor aqueous solution utilizing the method to obtain, long-chain fat amine and short-chain fat amine are fully combined with Cadmium oxide, and passivation is carried out to the surface of Cadmium oxide, when obtained Cd precursor aqueous solution is brown yellow transparent liquid, illustrate that Cd produces coordination by CdO solid form and oleic acid, aliphatic amide etc., change ionic state into.
S200 provides selenium precursor aqueous solution
According to embodiments of the invention, this selenium precursor aqueous solution comprises selenium powder, long-chain fat amine and short-chain fat amine.Because the amido on Se and aliphatic amide is all electron rich group, the two does not carry out coordination in theory, but in fact, aliphatic amide is added iff in Cadmium oxide, Cd precursor aqueous solution and Se precursor aqueous solution diffusive mixing extremely uniform time can be extended, cause the CdSe quantum dot monodispersity of synthesizing to be deteriorated, therefore, in Se precursor aqueous solution, add the aliphatic amide consistent with Cd precursor aqueous solution concentration.
According to some embodiments of the present invention, the mol ratio of selenium powder, long-chain fat amine and short-chain fat amine is 1:(2-5): (2-5).Thus, in this quality than under scope, selenium powder is easy to be combined with long-chain fat amine and short-chain fat amine, and the synergy of long-chain fat amine and short-chain fat amine well, contributes to the stably growth of crystal, obtains CdSe crystal monodispersity good.According to preferred embodiments more of the present invention, the mol ratio of selenium powder, long-chain fat amine and short-chain fat amine is 1:3:3.Thus, the synergy of long-chain fat amine and short-chain fat amine is better, more contributes to the stably growth of crystal, obtains CdSe crystal monodispersity better.
According to some embodiments of the present invention, selenium precursor aqueous solution is obtained by following steps: selenium powder, long-chain fat amine and short-chain fat amine are mixed, obtain the second mixture; Second mixture is mixed with tri-n-octyl phosphine, utilizes 1-octadecylene to dissolve, obtain the second mixed solution; Described second mixed solution is carried out heat treated, obtains selenium precursor aqueous solution.Thus, the selenium precursor aqueous solution utilizing the method to obtain, tri-n-octyl phosphine is fully combined with selenium powder, and passivation is carried out to the surface of selenium powder, when obtained Se precursor aqueous solution is colourless transparent liquid, illustrate that Se produces coordination by Se powder solid form and tri-n-octyl phosphine, change ionic state into.
According to some embodiments of the present invention, sampler is utilized to provide selenium precursor aqueous solution and cadmium precursor aqueous solution respectively.Thus, by controlling the sample introduction speed of sampler, accurately the reaction times is controlled.
According to some embodiments of the present invention, sampler provides cadmium precursor aqueous solution and selenium precursor aqueous solution with the speed of 50 μ L/min.Thus, provide selenium precursor aqueous solution and cadmium precursor aqueous solution with this speed, the two can minipool, fully reacts, obtains CdSe quantum dots, and the output of CdSe quantum dots is large, and productive rate is high.
S300 combination treatment
According to embodiments of the invention, cadmium precursor aqueous solution and selenium precursor aqueous solution are carried out combination treatment, obtains precursor aqueous solution mixture.Thus, cadmium precursor aqueous solution is fully contacted with selenium precursor aqueous solution, be convenient to subsequent heat and generate CdSe quantum dots.
S400 heat treated
According to embodiments of the invention, precursor aqueous solution mixture is carried out heat treated, obtains quantum dot solution, wherein, containing described CdSe quantum dots in quantum dot solution.Thus, by heating, cadmium precursor aqueous solution and selenium precursor aqueous solution are reacted, obtain CdSe quantum dots.
According to embodiments of the invention, the temperature of oil bath is not particularly limited, as long as make cadmium precursor aqueous solution and selenium precursor aqueous solution react, obtains CdSe quantum dots, can adjust according to the boiling point of the long-chain fat amine adopted and short-chain fat amine.According to some embodiments of the present invention, heat treated utilizes oil bath under the condition of 210-280 degree Celsius, and heating 30-50 carries out second.Mixing solutions before utilizing ultra violet lamp to heat in experiment, not obvious exciting light, the liquid of deriving after utilizing ultra violet lamp to heat, obviously can see fluorescence excitation, illustrate after reacting by heating, CdSe quantum dot generates.According to preferred embodiments more of the present invention, when short-chain fat amine is amino dodecane, when long-chain fat amine is oleyl amine, under the condition of 260-280 degree Celsius, the CdSe quantum dot of gained is the sample be all better than from monodispersity, fluorescent yield or degree of crystallinity 210-250 degrees celsius.This is the short-chain fat amine owing to choosing in an experiment is amino dodecane, its boiling point is 249 degrees Celsius, when temperature of reaction is 260-280 degree Celsius, amino dodecane can promote crystal blast nucleation below 250 degrees Celsius, and plane of crystal is departed near 250 degrees Celsius, and then oleyl amine and plane of crystal coordination stable growth, short-chain fat amine and the effect of long-chain fat amine coordinated regulation are made the most of the advantage.
According to some embodiments of the present invention, the method comprises further: by described quantum dot solution and the first precipitant mix, to obtain the first precipitation; By described first precipitation be dissolved in organic solvent, and with the second precipitant mix, to obtain the second precipitation; And described second precipitation is dried grinding, to obtain powder of cadmium selenide quanta dots capable.Thus, by precipitation agent process quantum dot solution, extract quantum dot powder, simple, convenient, and the quantum dot powder purity obtained is high.According to some embodiments of the present invention, the scope of uv-visible absorption spectra first excitation peak of CdSe quantum dot powder is 500-640 nanometer, the peak width at half height of fluorescence emission peak is 30 ran, thus, utilize uv-visible absorption spectra to detect the purity of CdSe quantum dot powder.
According to some embodiments of the present invention, the first precipitation agent is dehydrated alcohol, and the second precipitation agent is acetone.Thus, sedimentation effect is good, and the quantum dot powder purity obtained is high.
According to some embodiments of the present invention, the method preparing CdSe quantum dots of the present invention can be undertaken by microscale reactor, wherein, the structural representation of microscale reactor as shown in Figure 2, this microscale reactor comprises substrate, cover plate, and wherein, the base material of substrate is processed with " Y type " charging groove and " S type " micro mixer, " Y type " charging access recess bore is 500-2000 micron " Y type " charging notch end and " S type " micro mixer, and front end is connected; " Y type " charging access recess bore is 500-2000 micron, " S type " micro mixer, outlet pipe internal diameter is that 300-1200 micron cover plate fits tightly and sealed by groove at the upper surface of substrate, wherein, " Y type " charging groove and " S type " micro mixer, material be tetrafluoroethylene, glass or silica glass.Utilize microscale reactor to prepare CdSe quantum dots, accurately can control the reaction times, and, the microchannel of microscale reactor can efficient heat transfer, contributes to temperature adjusting, and then, by regulating raw material composition, reaction times and temperature, can continuous production different-waveband quantum dot.
Particularly, above-mentioned microreactor is utilized to prepare the method for CdSe quantum dots as follows: to utilize syringe respectively to extract cadmium precursor solution and selenium precursor solution, utilize syringe pump to micro mixer charging, in micro mixer after mixing, mixing solutions is imported in oil bath heater and heats, to derive and the red solution collected is CdSe quantum dots solution.
According to method of the present invention, method of the present invention is utilized to prepare CdSe quantum dots, have simple to operate, easy to make, regulate and control the advantages such as accurate, and, the present invention utilizes mixing-in fat amine coordinated regulation nucleation and growth, contribute to improving the monodispersity of quantum dot, and can continuous seepage, be conducive to the suitability for industrialized production of quantum dot.
Below with reference to specific embodiment, the present invention will be described, it should be noted that, these embodiments are only illustrative, and can not be interpreted as limitation of the present invention.
Embodiment 1
In the present embodiment, only utilize oleyl amine for coordination amine, detect and synthesize CdSe quantum dot and optical parametric thereof at different temperatures.Concrete grammar is as follows:
(1) feed oxygen cadmium (CdO) 0.0161g is taken with beaker, oleyl amine (OLA) 4.0126g, and in beaker, add 0.2mL oleic acid (OA) and 1.25g trioctylphosphine (TOPO), utilize 1-octadecylene (ODE) diluted system to 15mL; By beaker in 150 DEG C of heating 1 hour, obtain brown yellow transparent liquid as Cd precursor solution.
(2) take raw material selenium powder (Se) 0.2632g with beaker, oleyl amine (OLA) 5.3502g, and in beaker, add 3mL tri-n-octyl phosphine (TOP), utilize 1-octadecylene (ODE) diluted system to 20mL; By beaker in 90 DEG C of heating 15 minutes, obtain colourless transparent liquid as Se precursor solution.
(3) utilize syringe respectively to extract Cd precursor solution and Se precursor solution 12mL, utilize syringe pump with 50 μ L/min by tetrafluoroethylene pipeline to micro mixer charging.
(4) the mixed mixture of micro mixer utilizes polyfluortetraethylene pipe to import in oil bath by mixing solutions, react 40 seconds, the temperature of oil bath is successively elevated to 280 DEG C with 10 DEG C for interval from 210 DEG C, each temperature-stable connects sample 15 minutes after 20 minutes, derive and the red solution collected is CdSe quantum dot solution.
(5) add precipitation agent dehydrated alcohol in the CdSe quantum dot solution of step (4) gained, the volume ratio of quantum dot solution and precipitation agent is 1:4, produces flocks, centrifugation.
(6) be dissolved in 5mL normal hexane by the throw out that step (5) obtains, then add 20mL acetone, produce flocks, centrifugation, dries the throw out obtained and grinds, and obtains CdSe quantum dot powder.
(7) uv-visible absorption spectra is utilized to detect the CdSe quantum dot powder that step (6) obtains, the CdSe quantum dot uv-visible absorption spectra first excitation peak peak value synthesized under differing temps as shown in Figure 3, this CdSe quantum dot uv-visible absorption spectra first excitation peak scope is between 520nm to 540nm, when temperature of reaction is 250 DEG C, uv-visible absorption spectra first excitation peak peak value is minimum, for 524nm, fluorescence spectrum peak width at half height is between 30nm to 60nm.
(8) fluorescent reflection spectrum is utilized to detect the CdSe quantum dot powder that step (6) obtains, the half-value width collection of illustrative plates of the CdSe quantum dot fluorescent reflection spectrum synthesized under differing temps as shown in Figure 4, oleyl amine is adopted to be coordination amine, along with the rising of temperature, there is Red Shift Phenomena in the first excitation peak peak value of ultraviolet-visible absorption spectroscopy, this is mainly because temperature raises, contribute to the speed accelerating blast nucleation and crystal growth, high temperature contributes to Ostwald slaking simultaneously, CdSe quantum dot particle diameter is finally caused to become large, characteristic peak red shift.
Embodiment 2
In the present embodiment, only utilize n-Laurylamine for coordination amine, detect and synthesize CdSe quantum dot and optical parametric thereof at different temperatures, specific as follows:
(1) feed oxygen cadmium (CdO) 0.0161g is taken with beaker, n-Laurylamine (DDA) 2.7804g, and in beaker, add 0.2mL oleic acid (OA) and 1.25g trioctylphosphine (TOPO), utilize 1-octadecylene (ODE) diluted system to 15mL; By beaker in 150 DEG C of heating 1 hour, obtain brown yellow transparent liquid as Cd precursor solution.
(2) raw material selenium powder (Se) 0.2632g is taken with beaker, n-Laurylamine (DDA) 3.7032g, and in beaker, add 3mL tri-n-octyl phosphine (TOP), utilize 1-octadecylene (ODE) diluted system to 20mL; By beaker in 90 DEG C of heating 15 minutes, obtain colourless transparent liquid as Se precursor solution.
(3) utilize syringe respectively to extract Cd precursor solution and Se precursor solution 12mL, utilize syringe pump with 50 μ L/min by tetrafluoroethylene pipeline to micro-hybrid charging.
(4) the mixed mixture of micro mixer utilizes tetrafluoroethylene pipeline to import in oil bath by mixing solutions, react 40 seconds, the temperature of oil bath is successively elevated to 280 DEG C with 10 DEG C for interval from 210 DEG C, each temperature-stable connects sample 15 minutes after 20 minutes, derive and the red solution collected is CdSe quantum dot solution.
(5) add precipitation agent dehydrated alcohol in the CdSe quantum dot solution of step (4) gained, the volume ratio of quantum dot solution and precipitation agent is 1:4, produces flocks, centrifugation.
(6) be dissolved in 5mL normal hexane by the throw out that step (5) obtains, then add 20mL acetone, produce flocks, centrifugation, dries the throw out obtained and grinds, and obtains CdSe quantum dot powder.
(7) uv-visible absorption spectra is utilized to detect CdSe quantum dot powder, this CdSe quantum dot uv-visible absorption spectra first excitation peak scope is between 570nm to 620nm, when temperature of reaction is 250 DEG C, uv-visible absorption spectra first excitation peak peak value is maximum, for 613nm, fluorescence spectrum peak width at half height is between 30nm to 40nm.Can find from Fig. 4, amino dodecane is adopted to be coordination amine, along with the rising of temperature, there is Red Shift Phenomena in the first excitation peak peak value of ultraviolet-visible absorption spectroscopy, this mainly raises due to temperature, and contribute to the speed accelerating blast nucleation and crystal growth, high temperature contributes to Ostwald slaking simultaneously, CdSe quantum dot particle diameter is finally caused to become large, characteristic peak red shift.Simultaneously, the optical characterisation result of contrast amino dodecane and oleyl amine, we can find, the CdSe quantum dot utilizing amino dodecane to regulate and control preparation is prepared than oleyl amine regulation and control, under same temperature of reaction, all there is red shift in characteristic peak, illustrates that short-chain fat amine can accelerate the speed of nucleation and growth, particularly growth velocity, makes the size of CdSe quantum dot become large.
Embodiment 3
In the present embodiment, utilize mol ratio to be coordination amine for 1:1 oleyl amine and n-Laurylamine mixed amine, detect and synthesize CdSe quantum dot and optical parametric thereof at different temperatures, specific as follows:
(1) feed oxygen cadmium (CdO) 0.0161g is taken with beaker, oleyl amine (OLA) 2.0063g, n-Laurylamine (DDA) 1.3902g, and in beaker, add 0.2mL oleic acid (OA) and 1.25g trioctylphosphine (TOPO), utilize 1-octadecylene (ODE) diluted system to 15mL; By beaker in 150 DEG C of heating 1 hour, obtain brown yellow transparent liquid as Cd precursor solution.
(2) raw material selenium powder (Se) 0.2632g is taken with beaker, oleyl amine (OLA) 2.6751g, n-Laurylamine (DDA) 1.8516g, and in beaker, add 3mL tri-n-octyl phosphine (TOP), utilize 1-octadecylene (ODE) diluted system to 20mL; By beaker in 90 DEG C of heating 15 minutes, obtain colourless transparent liquid as Se precursor solution.
(3) utilize syringe respectively to extract Cd precursor solution and Se precursor solution 12mL, utilize syringe pump with 50 μ L/min by tetrafluoroethylene pipeline to micro-hybrid charging.
(4) the mixed mixture of micro mixer utilizes tetrafluoroethylene pipeline to import in oil bath by mixing solutions, react 40 seconds, the temperature of oil bath is successively elevated to 280 DEG C with 10 DEG C for interval from 210 DEG C, each temperature-stable connects sample 15 minutes after 20 minutes, derive and the red solution collected is CdSe quantum dot solution.
(5) add precipitation agent dehydrated alcohol in the CdSe quantum dot solution of step (4) gained, the volume ratio of quantum dot solution and precipitation agent is 1:4, produces flocks, centrifugation.
(6) throw out that step (5) obtains is dissolved in 5mL normal hexane, add 20mL acetone again, produce flocks, centrifugation, the throw out obtained is dried and grinds, obtain CdSe quantum dot powder, wherein, when temperature of reaction is 270 DEG C, the TEM picture of CdSe quantum dots as shown in Figure 6, from figure, we can find out that gained CdSe quantum dot is spherical in shape, and size topography uniformity is good, size, at about 5nm, especially merits attention and is, CdSe quantum dot lattice is clear neatly distinguishable, illustrates that degree of crystallinity is better.
(7) uv-visible absorption spectra is utilized to detect CdSe quantum dot powder, this CdSe quantum dot uv-visible absorption spectra as shown in Figure 5, first excitation peak scope is between 540nm to 560nm, fluorescence spectrum peak width at half height is between 25nm to 35nm, when temperature of reaction is 280 DEG C, fluorescence spectrum peak width at half height is minimum, for 27.6nm, this explanation utilizes mixed amine to regulate and control, amino dodecane can be utilized to promote, and CdSe quantum dot blast nucleogenesis is in oleyl amine stable crystal growth simultaneously, and gained quantum single point dispersiveness has had and increases substantially.
Can find from Fig. 4, mixed amine is adopted to be coordination amine, along with the rising of temperature, there is Red Shift Phenomena in the first excitation peak peak value of ultraviolet-visible absorption spectroscopy, this mainly raises due to temperature, and contribute to the speed accelerating blast nucleation and crystal growth, high temperature contributes to Ostwald slaking simultaneously, CdSe quantum dot particle diameter is finally caused to become large, characteristic peak red shift.Simultaneously, owing to there is amino dodecane and oleyl amine in mixed amine simultaneously, from optical characterisation result, we can find, mixed amine is utilized to regulate and control the CdSe quantum dot of preparation, under same temperature of reaction, characteristic peak, between amino dodecane regulation and control and oleyl amine regulate and control, embodies amino dodecane and the effect of oleyl amine synergic adjustment in mixed amine.
To sum up, relative to only adopting long-chain fat amine or short-chain fat amine to press as coordination, mixing-in fat amine is adopted to press as coordination, can coordinated regulation nucleation and growth better, the monodispersity of the quantum dot obtained is better, and can continuous seepage, has the industrial production prospect of quantification.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, identical embodiment or example are not necessarily referred to the schematic representation of above-mentioned term.And the specific features of description, structure, material or feature can combine in an appropriate manner in any one or more embodiment or example.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (10)
1. prepare a method for CdSe quantum dots, it is characterized in that, comprising:
There is provided cadmium precursor aqueous solution, wherein, described cadmium precursor aqueous solution comprises Cadmium oxide, long-chain fat amine and short-chain fat amine;
There is provided selenium precursor aqueous solution, wherein, described selenium precursor aqueous solution comprises selenium powder, long-chain fat amine and short-chain fat amine;
Described cadmium precursor aqueous solution and described selenium precursor aqueous solution are carried out combination treatment, to obtain precursor aqueous solution mixture; And described precursor aqueous solution mixture is carried out heat treated, to obtain quantum dot solution, wherein, containing described CdSe quantum dots in described quantum dot solution.
2. method according to claim 1, is characterized in that, the mol ratio of described Cadmium oxide, described long-chain fat amine and described short-chain fat amine is 1:(50-70): (50-70) preferably, is 1:60:60.
3. method according to claim 1, is characterized in that, the mol ratio of described selenium powder, described long-chain fat amine and described short-chain fat amine is 1:(2-5): (2-5) preferably, is 1:3:3.
4. method according to claim 1, is characterized in that, described short-chain fat amine is at least one being selected from octylame, ten amine and amino dodecane.
5. method according to claim 1, is characterized in that, described long-chain fat amine is at least one being selected from tetradecy lamine, cetylamine, stearylamine and oleyl amine.
6. method according to claim 1, is characterized in that, described cadmium precursor aqueous solution is obtained by following steps:
Cadmium oxide, long-chain fat amine and short-chain fat amine are mixed, obtains the first mixture;
Described first mixture is mixed with oleic acid and trioctylphosphine, utilizes 1-octadecylene to dissolve, to obtain the first mixed solution; And
Described first mixed solution is carried out heat treated, to obtain cadmium precursor aqueous solution.
7. method according to claim 1, is characterized in that, described selenium precursor aqueous solution is obtained by following steps:
Selenium powder, long-chain fat amine and short-chain fat amine are mixed, obtains the second mixture;
Described second mixture is mixed with tri-n-octyl phosphine, utilizes 1-octadecylene to dissolve, to obtain the second mixed solution; And
Described second mixed solution is carried out heat treated, to obtain selenium precursor aqueous solution.
8. method according to claim 1, is characterized in that, utilizes sampler to provide described selenium precursor aqueous solution and described cadmium precursor aqueous solution respectively,
Optionally, described sampler provides described cadmium precursor aqueous solution and described selenium precursor aqueous solution with the speed of 50 μ L/min.
9. method according to claim 1, is characterized in that, described heat treated utilizes oil bath under the condition of 210-280 degree Celsius, and heating 30-50 carries out, preferably, under the condition of 260-280 degree Celsius second.
10. method according to claim 1, is characterized in that, comprises further:
By described quantum dot solution and the first precipitant mix, to obtain the first precipitation;
By described first precipitation be dissolved in organic solvent, and with the second precipitant mix, to obtain the second precipitation; And
Described second precipitation is dried grinding, to obtain powder of cadmium selenide quanta dots capable,
Optionally, described first precipitation agent is dehydrated alcohol, and described second precipitation agent is acetone.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108538953A (en) * | 2018-03-30 | 2018-09-14 | 深圳华中科技大学研究院 | A kind of solar blind ultraviolet detector and preparation method thereof based on ZnS quantum dots |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053810A1 (en) * | 2000-12-28 | 2002-07-11 | Quantum Dot Corporation | Flow synthesis of quantum dot nanocrystals |
| CN101264868A (en) * | 2008-03-05 | 2008-09-17 | 河南大学 | Method for preparing selenium-containing compound nano crystal |
-
2015
- 2015-08-21 CN CN201510518400.6A patent/CN105038798A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053810A1 (en) * | 2000-12-28 | 2002-07-11 | Quantum Dot Corporation | Flow synthesis of quantum dot nanocrystals |
| CN101264868A (en) * | 2008-03-05 | 2008-09-17 | 河南大学 | Method for preparing selenium-containing compound nano crystal |
Non-Patent Citations (1)
| Title |
|---|
| 田震昊: "微通道中CdSe量子点的可控合成", 《清华大学本科毕业论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108538953A (en) * | 2018-03-30 | 2018-09-14 | 深圳华中科技大学研究院 | A kind of solar blind ultraviolet detector and preparation method thereof based on ZnS quantum dots |
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