CN106635022A - Method for preparing oil-soluble selenium or telluride semiconductor quantum dot without phosphine through dissolving chalcogenide oxide by alkanethiol - Google Patents
Method for preparing oil-soluble selenium or telluride semiconductor quantum dot without phosphine through dissolving chalcogenide oxide by alkanethiol Download PDFInfo
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- CN106635022A CN106635022A CN201610842555.XA CN201610842555A CN106635022A CN 106635022 A CN106635022 A CN 106635022A CN 201610842555 A CN201610842555 A CN 201610842555A CN 106635022 A CN106635022 A CN 106635022A
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Abstract
The invention belongs to the technical field of fluorescent quantum dot preparation, concretely relates to a method for preparing oil-soluble selenium or telluride semiconductor quantum dot without phosphine, and especially relates to a method for preparing a selenium or tellurium precursor by reducing and dissolving selenium dioxide or tellurium dioxide as raw materials in alkanethiol and preparing a high-quality functional selenium or telluride semiconductor quantum dots by utilizing the precursor. The selenium or tellurium dioxide is dissolved by using alkanethiol, so as to obtain a selenium or tellurium solution. The alkanethiol and the selenium or tellurium dioxide used in the invention are all common stable compounds, are low in price, green and environment-friendly. The prepared precursor is high in activity, and can be used for preparing various functional selenium or telluride quantum dots under a relatively mild condition; the method can effectively reduce the preparation cost, meanwhile the environmental pollution is reduced, and the method is significant on the industrial production of the selenium or telluride quantum dots and the relevant LED industry.
Description
Technical field
The invention belongs to fluorescence quantum preparing technical field, and in particular to one kind prepares oil-soluble selenium or tellurides without phosphine
The method of semiconductor-quantum-point, more particularly to one kind are reduced molten as raw material with selenium dioxide or tellurium dioxide in alkyl hydrosulfide
The method of solution prepares selenium or tellurium presoma, and prepares high-quality feature selenium or tellurides as semiconductor quantum dot using this forerunner's body
Method.
Background technology
Fluorescence selenium or tellurides as semiconductor quantum dot have narrow fluorescence emission spectrum, extensive colour gamut and good reason
Change stability, illumination display field most one of technology of competitiveness is had become based on the Novel LED light source of such quantum dot.
As people increasingly increase the demand of selenium or tellurides as semiconductor quantum dot, the green batch of selenium or tellurides as semiconductor quantum dot
Amount production becomes a problem demanding prompt solution.At present, develop most ripe, be also most classical to prepare selenium or tellurides as semiconductor
The method of quantum dot, surely belongs to hot injection.Hot injection is employed and is rapidly injected in metal front liquid solution in hot conditions
The operating technology of nonmetallic presoma.This method growth mechanism clearly, can effectively by the nucleation and growth mistake of quantum dot
Journey is separated, so as to ensure size uniformity, the stable performance of quantum dot.In operation, a crucial step be prepare it is non-
Metal (selenium or tellurium) presoma.Mainly use the organic phosphines such as tributylphosphine, tri octyl phosphine to dissolve in selenium powder, tellurium powder, then will
It is expelled in the source metal solution of high temperature.But these organic phosphonate reagents are not only harmful to human body, environment, and price are polluted
It is expensive.Additionally, organic phosphonate reagent is easily oxidized to air-sensitive, so whole preparation process is required for entering in glove box
OK, these all considerably increase the difficulty and cost for preparing quantum dot, limit the industrial applications of this preparation method.With
People constantly study, it is a series of without phosphine prepare selenium or the method for tellurides as semiconductor quantum dot is developed.Such as exist
By the advance heating for dissolving of selenium powder in high boiling ligand solvent or non-coordinating solvent, selenide quantum dots are prepared.This method will
High reaction temperature and longer dissolution time are asked, time and energy cost are high.Simultaneously because the high-melting-point of tellurium powder and weak non-gold
Attribute, such method is not particularly suited for the preparation of telluride quantum dots.Additionally, in aqueous preparing cadmium selenide, cadmium telluride
Method is also developed.This method mainly uses sodium borohydride reduction selenium powder, tellurium powder, and selenium is first prepared in aqueous
Sodium hydride, sodium hydrogen telluride solution, further with sodium hydrogen selenide, the sodium hydrogen telluride for preparing as non-metal source, addition is ready to
The presoma of the aqueous solution containing cadmium in, by being heated to reflux preparing cadmium selenide, cadmium telluride quantum dot.Although this improvement has eliminated
Machine phosphonate reagent, but because the boiling point of water is relatively low, reaction temperature is limited, it usually needs and longer return time completes reaction.
It is unfavorable for the industrialized production of quantum dot.In addition, the method is present compared with big limitation, be only applicable to prepare the selenium containing cadmium and mercury or
Tellurides as semiconductor quantum dot.Therefore, development be applied to simultaneously selenium or tellurides as semiconductor quantum dot it is easy, efficient, environmentally friendly,
Low cost, can industrialized production synthetic method it is extremely urgent.
The content of the invention
The purpose of the present invention is exactly the selenium without phosphine or tellurium presoma for preparing a kind of cheap and simple, and using this forerunner's system
Standby oil-soluble selenium or tellurides as semiconductor quantum dot, i.e., with selenium dioxide or tellurium dioxide as raw material, by it in alkyl hydrosulfide
Reduction of dissolved, so as to obtain selenium or tellurium presoma, and prepares selenium or tellurides as semiconductor quantum dot using this forerunner's body.The present invention
Core content be the dioxide that dissolved selenium or tellurium are removed with alkyl hydrosulfide, obtain the solution of selenium or tellurium.
The present invention is raw material from selenium dioxide or tellurium dioxide, and alkyl hydrosulfide is reducing agent and ligand solvent.Wherein, institute
The reaction reagent low price that is related to, environmental friendliness, in atmosphere can be with stable existence；Prepare selenium or tellurium presoma process without
The glove box operation of strict anhydrous and oxygen-free is needed, it is dangerous little；Prepared presoma activity is high, may be implemented in compared with temperate condition
It is rapidly completed quantum dot preparation；Product quantum dot is functional, and with preferable experimental repeatability.Therefore, this method
Effectively reduce preparation cost and environment will not be damaged, be well suited for the industrialized production of quantum dot.
Specifically, step of the invention is as follows：
(1) under nitrogen protection, selenium dioxide is added into stirring and dissolving in alkyl hydrosulfide, obtains selenium precursor solution,
The concentration of selenium dioxide is 0.1～1mol/L；
(2) under nitrogen protection, tellurium dioxide is added in alkyl hydrosulfide, 100～200 DEG C of heating stirrings obtain tellurium
Precursor solution, the concentration of tellurium dioxide is 0.1～1mol/L；
(3) under nitrogen protection, source metal (one or more in cadmium source, lead source, mercury source, Yin Yuan, copper source) is added
To in the mixed solution of aliphatic amine or aliphatic acid with octadecylene, the concentration of source metal is 0.1～0.5mol/L, and 60～80 DEG C add
Thermal agitation dissolves source metal；Then 90～200 DEG C are warmed up to, selenium prepared by preceding step or tellurium presoma are added, dioxy
The mol ratio for changing selenium or tellurium dioxide and source metal is 1：1～1：10, continue to react 5～30 minutes, obtain selenium or tellurides half
Conductor quantum dot.
The method of the invention can be used to prepare CdSe, CdTe, PbTe, HgTe, Ag2Te、Cu2The various selenium such as Te or telluride
Thing semiconductor-quantum-point.
The cadmium source that said method is used can be Cd (Ac)2·2H2O、CdCl2·2H2O, CdO etc.；Lead source can be Pb
(Ac)2·2H2O、PbCl2, PbO etc.；Mercury source can be Hg (Ac)2·2H2O、HgCl2, HgO etc.；Silver-colored source can be Ag (Ac),
AgNO3, Ag (acac) etc.；Copper source can be Cu (Ac)2、CuCl2、Cu2O etc..Alkyl hydrosulfide can be spicy thioalcohol, dodecyl
Mercaptan, hexadecyl mercaptan, octadecyl sulphur etc..Aliphatic amine can be oleyl amine, hexadecylamine, octadecylamine etc..Fat
Fat acid can be oleic acid, stearic acid, tetradecylic acid etc..
Description of the drawings
Fig. 1 (a)：The transmission electron microscope photo of oil-soluble CdSe quantum dot prepared by embodiment 1, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 2.5nm；
Fig. 1 (b)：The UV absorption spectrogram of oil-soluble CdSe quantum dot prepared by embodiment 1, gained quantum dot is in visible ray
There is very strong absorption efficiency in region；
Fig. 1 (c)：The XRD spectra of oil-soluble CdSe quantum dot prepared by embodiment 1, gained quantum dot is cubic-crystal；
Fig. 2 (a)：The transmission electron microscope photo of oil-soluble CdTe quantum prepared by embodiment 3, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 2.2nm；
Fig. 2 (b)：The UV absorption (curve 1) and fluorescent emission spectrogram of oil-soluble CdTe quantum prepared by embodiment 3
(curve 2), gained quantum dot has very narrow UV absorption and fluorescent emission half-peak breadth；
Fig. 3 (a)：The transmission electron microscope photo of oil-soluble CdTe quantum prepared by embodiment 4, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 2.6nm；
Fig. 3 (b)：The UV absorption (curve 1) and fluorescent emission spectrogram of oil-soluble CdTe quantum prepared by embodiment 4
(curve 2), gained quantum dot has very narrow UV absorption and fluorescent emission half-peak breadth；
Fig. 4 (a)：The transmission electron microscope photo of oil-soluble CdTe quantum prepared by embodiment 5, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 3.2nm；
Fig. 4 (b)：The UV absorption (curve 1) and fluorescent emission spectrogram of oil-soluble CdTe quantum prepared by embodiment 5
(curve 2), gained quantum dot has very narrow UV absorption and fluorescent emission half-peak breadth；
Fig. 5 (a)：The transmission electron microscope photo of oil-soluble CdTe quantum prepared by embodiment 6, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 3.6nm；
Fig. 5 (b)：The UV absorption (curve 1) and fluorescent emission spectrogram of oil-soluble CdTe quantum prepared by embodiment 6
(curve 2), gained quantum dot has very narrow UV absorption and fluorescent emission half-peak breadth；
Fig. 6 (a)：The transmission electron microscope photo of oil-soluble HgTe quantum dots prepared by embodiment 7, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 1.9nm；
Fig. 6 (b)：The UV absorption spectrogram of oil-soluble HgTe quantum dots prepared by embodiment 7, gained quantum dot is in visible ray
There is very strong absorption efficiency in region；
Fig. 6 (c)：The XRD spectra of oil-soluble HgTe quantum dots prepared by embodiment 7, gained quantum dot is cubic-crystal；
Fig. 7 (a)：The transmission electron microscope photo of oil-soluble PbTe quantum dots prepared by embodiment 9, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 11.3nm；
Fig. 7 (b)：The XRD spectra of oil-soluble PbTe quantum dots prepared by embodiment 9, gained quantum dot is cubic-crystal；
Fig. 7 (c)：The UV absorption spectrogram of oil-soluble PbTe quantum dots prepared by embodiment 9, gained quantum dot is in visible ray
There is very strong absorption efficiency in region；
Fig. 8 (a)：Oil-soluble Cu prepared by embodiment 102The transmission electron microscope photo of Te quantum dots, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 4.3nm；
Fig. 8 (b)：Oil-soluble Cu prepared by embodiment 102The XRD spectra of Te quantum dots, gained quantum dot is hexagonal crystal shape；
Fig. 8 (c)：Oil-soluble Cu prepared by embodiment 102The UV absorption spectrogram of Te quantum dots, gained quantum dot is visible
There is very strong absorption efficiency in light region；
Fig. 9 (a)：Oil-soluble Ag prepared by embodiment 112The transmission electron microscope photo of Te quantum dots, gained quantum dot size is equal
Even, monodispersity is good, and average-size is 6.2nm；
Fig. 9 (b)：Oil-soluble Ag prepared by embodiment 112The UV absorption spectrogram of Te quantum dots, gained quantum dot is visible
There is very strong absorption efficiency in light region；
Fig. 9 (c)：Oil-soluble Ag prepared by embodiment 112The XRD spectra of Te quantum dots, gained quantum dot is monoclinic form.
Specific embodiment
With reference to embodiment, the present invention is further elaborated, rather than to be limited the invention with this.
Embodiment 1
By 0.11g (1mmol) SeO2Powder is added in 2mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats 3 times.It is stirred at room temperature under nitrogen protection, treats SeO2All dissolving obtains yellow solution to powder, and the solution is made
It is used for selenides for selenium presoma and synthesizes semiconductor-quantum-point.
By 0.27g (1mmol) Cd (AC)2·2H2O is added in 1mL oleic acid and 9mL octadecylene mixed solutions.Reaction system
Vacuumize, lead to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, to Cd (AC)2·
2H2O dissolves.Then in N2Solution is warmed up into 150 DEG C under gas shielded, selenium presoma prepared above is added, 150 DEG C after
Continuous reaction 10 minutes, as shown in figure 1, obtaining CdSe semiconductor-quantum-points.
Embodiment 2
By 0.06g (0.5mmol) SeO2Powder is added in 5mL lauryl mercaptans, and system is led to after vacuumizing 10 minutes
Enter nitrogen, repeat 3 times.It is stirred at room temperature under nitrogen protection, treats SeO2All dissolving obtains yellow solution to powder, the solution
It is used for selenides as selenium presoma and synthesizes semiconductor-quantum-point.
By 0.14g (0.5mmol) Cd (AC)2·2H2O is added in 1mL oleic acid and 9mL octadecylene mixed solutions.Reactant
System vacuumizes, leads to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, to Cd
(AC)2·2H2O dissolves.Then in N2Solution is warmed up into 200 DEG C under gas shielded, selenium presoma prepared above is added,
200 DEG C are continued to react 30 minutes, obtain CdSe semiconductor-quantum-points.
Embodiment 3
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amines and 5mL octadecylenes.Reactant
System vacuumizes, leads to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, by CdCl2·
2H2O dissolves, and obtains milky white solution.Then in N2Tellurium presoma prepared above is injected under gas shielded, reaction 10min stops
Heating, as shown in Fig. 2 obtaining the CdTe semiconductor-quantum-points with green-fluorescent emission.50mg had into green emission
CdTe quantum is added in 0.5mL acrylic type light-cured resins, is stirred.Mixture is covered in into launch wavelength is
The GaInN chips (5mm × 5mm) of 365nm.After ultraviolet light polymerization, there can be the LED component of green emission.
Embodiment 4
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amines and 5mL octadecylenes.Reactant
System vacuumizes, leads to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, by CdCl2·
2H2O dissolves, and obtains milky white solution.Then in N2Temperature is risen into 130 DEG C under gas shielded, tellurium presoma prepared above is noted
Enter, reaction 10min stops heating, as shown in figure 3, obtaining the CdTe semiconductor-quantum-points with yellow fluorescence transmitting.By 50mg
CdTe quantum with yellow emission is added in 0.5mL acrylic type light-cured resins, is stirred.Mixture is covered
In the GaInN chips (5mm × 5mm) that launch wavelength is 365nm.After ultraviolet light polymerization, there can be the LED component of yellow emission
Embodiment 5
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amines and 5mL octadecylenes.Reactant
System vacuumizes, leads to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, by CdCl2·
2H2O dissolves, and obtains milky white solution.Then in N2Temperature is risen into 140 DEG C under gas shielded, tellurium presoma prepared above is noted
Enter, reaction 10min stops heating, as shown in figure 4, obtaining the CdTe semiconductor-quantum-points with fluorescent orange.
Embodiment 6
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amines and 5mL octadecylenes.Reactant
System vacuumizes, leads to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, by CdCl2·
2H2O dissolves, and obtains milky white solution.Then in N2Temperature is risen into 185 DEG C under gas shielded, tellurium presoma prepared above is noted
Enter, reaction 10min stops heating, as shown in figure 5, obtaining the CdTe semiconductor-quantum-points with red fluorescence.50mg is had
The CdTe quantum of red emission is added in 0.5mL acrylic type light-cured resins, is stirred.Mixture is covered in and is sent out
The GaInN chips (5mm × 5mm) of a length of 365nm of ejected wave.After ultraviolet light polymerization, there can be the LED component of red emission
Embodiment 7
By the CdTe quantum with green emission prepared in 50mg embodiments 3 and the tool prepared in 50mg embodiments 6
The CdTe quantum for having red emission is added in 0.5mL acrylic type light-cured resins, is stirred.Mixture is covered in
Launch wavelength is the GaInN blue chips (5mm × 5nm) of 450nm.After ultraviolet light polymerization, can be based on three primary colours with white
Photoemissive LED component.
Embodiment 8
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.272g (1mmol) HgCl2In being added to the mixed solution of 8mL oleyl amines and 2mL octadecylenes.Reaction system is taken out very
Empty, logical nitrogen 3 times, every time 10 minutes.Then it is heated to 80 DEG C under vacuum to react 30 minutes, by HgCl2Dissolving, obtains
Milky white solution.Then in N2Solution is warmed up into 100 DEG C under gas shielded, Te presomas prepared above are injected, reaction
5min stops heating, as shown in fig. 6, obtaining HgTe semiconductor-quantum-points.
Embodiment 9
By 0.01g (0.05mmol) TeO2Powder is added in 1mL lauryl mercaptans, and system is led to after vacuumizing 10 minutes
Enter nitrogen, repeat three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to
Room temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.136g (0.5mmol) HgCl2In being added to the mixed solution of 8mL oleyl amines and 2mL octadecylenes.Reaction system is taken out
Vacuum, logical nitrogen 3 times, every time 10 minutes.Then it is heated to 80 DEG C under vacuum to react 30 minutes, by HgCl2Dissolving, obtains
To milky white solution.Then in N2Solution is warmed up into 100 DEG C under gas shielded, Te presomas prepared above are injected, reaction
5min stops heating, obtains HgTe semiconductor-quantum-points.
Embodiment 10
By 0.16g (1mmol) TeO2Powder is added in 1mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.278g (1mmol) PbCl2In being added to the mixed solution of 3mL oleic acid, 3mL oleyl amines and 4mL octadecylenes.Reaction
System is vacuumized, leads to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, by PbCl2
Dissolving, obtains transparent colourless solution.Then in N2Solution is warmed up into 150 DEG C under gas shielded, by tellurium presoma prepared above
Injection, reaction 7min stops heating, as shown in fig. 7, obtaining PbTe semiconductor-quantum-points.
Embodiment 11
By 0.16g (1mmol) TeO2Powder is added in 1mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.19g (1.4mmol) CuCl2In being added to the mixed solution of 5mL oleyl amines and 5mL octadecylenes.Reaction system is taken out
Vacuum, logical nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum to react 30 minutes, by CuCl2Dissolving.
Then in N2Temperature is risen into 180 DEG C under gas shielded, tellurium presoma prepared above is injected, reaction 15min stops heating, such as
Shown in Fig. 8, Cu is obtained2Te semiconductor-quantum-points.
Embodiment 12
By 0.16g (1mmol) TeO2Powder is added in 1mL lauryl mercaptans, and system is passed through after vacuumizing 10 minutes
Nitrogen, repeats three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to room
Temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.34g (2mmol) AgNO3In being added to the mixed solution of 8mL oleyl amines and 2mL octadecylenes.Reaction system is taken out very
Empty, logical nitrogen 3 times, every time 10 minutes.Then under nitrogen protection solution is warmed up into 180 DEG C, by tellurium forerunner prepared above
Body injects, and reaction 20min stops heating, as shown in figure 9, obtaining Ag2Te semiconductor-quantum-points.
Embodiment 13
By 0.08g (0.5mmol) TeO2Powder is added in 5mL lauryl mercaptans, and system is led to after vacuumizing 10 minutes
Enter nitrogen, repeat three times.Under nitrogen protection 100 DEG C of stirrings, treat TeO2All dissolving obtains orange solution to powder, is down to
Room temperature.The solution is used to synthesize semiconductor-quantum-point as tellurium presoma.
By 0.17g (1mmol) AgNO3In being added to the mixed solution of 8mL oleyl amines and 2mL octadecylenes.Reaction system is taken out very
Empty, logical nitrogen 3 times, every time 10 minutes.Then under nitrogen protection solution is warmed up into 180 DEG C, by tellurium forerunner prepared above
Body injects, and reaction 10min stops heating, obtains Ag2Te semiconductor-quantum-points.
Claims (5)
- It is 1. a kind of that the method that sulfur family oxide is realized preparing selenium or tellurides as semiconductor quantum dot without phosphine is dissolved by alkyl hydrosulfide, Its step is as follows：(1) under nitrogen protection, selenium dioxide is added into stirring and dissolving in alkyl hydrosulfide, obtains selenium precursor solution, dioxy The concentration for changing selenium is 0.1～1mol/L；(2) under nitrogen protection, tellurium dioxide is added in alkyl hydrosulfide, 100～200 DEG C of heating stirrings obtain tellurium forerunner Liquid solution, the concentration of tellurium dioxide is 0.1～1mol/L；(3) under nitrogen protection, source metal is added in the mixed solution of aliphatic amine or aliphatic acid with octadecylene, source metal Concentration be 0.1～0.5mol/L, 60～80 DEG C of heating stirrings dissolve source metal；Then 90～200 DEG C are warmed up to, by step (1) or the selenium for preparing of step (2) or tellurium presoma are added, the mol ratio of selenium dioxide or tellurium dioxide and source metal is 1：1～ 1：10, continue to react 5～30 minutes, obtain selenium or tellurides as semiconductor quantum dot.
- 2. one kind as claimed in claim 1 dissolves sulfur family oxide and realizes preparing selenium or tellurides half without phosphine by alkyl hydrosulfide The method of conductor quantum dot, it is characterised in that：Obtain CdSe, CdTe, PbTe, HgTe, Ag2Te or Cu2Te semiconductor-quantum-points.
- 3. one kind as claimed in claim 1 dissolves sulfur family oxide and realizes preparing selenium or tellurides half without phosphine by alkyl hydrosulfide The method of conductor quantum dot, it is characterised in that：Cadmium source is Cd (Ac)2·2H2O、CdCl2·2H2O or CdO；Lead source is Pb (Ac)2·2H2O、PbCl2Or PbO；Mercury source is Hg (Ac)2·2H2O、HgCl2Or HgO；Silver-colored source is Ag (Ac), AgNO3Or Ag (acac)；Copper source is Cu (Ac)2、CuCl2Or Cu2O。
- 4. one kind as claimed in claim 1 dissolves sulfur family oxide and realizes preparing selenium or tellurides half without phosphine by alkyl hydrosulfide The method of conductor quantum dot, it is characterised in that：Alkyl hydrosulfide is spicy thioalcohol, lauryl mercaptan, hexadecyl mercaptan or 18 Alkyl sulfide；Aliphatic amine is oleyl amine, hexadecylamine or octadecylamine；Aliphatic acid is oleic acid, stearic acid or tetradecylic acid.
- 5. one kind as claimed in claim 1 dissolves sulfur family oxide and realizes preparing selenium or tellurides half without phosphine by alkyl hydrosulfide The method of conductor quantum dot, it is characterised in that：Source metal is one or more in cadmium source, lead source, mercury source, Yin Yuan, copper source.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416777A (en) * | 2017-07-31 | 2017-12-01 | 吉林大学 | A kind of nanocrystalline method of no phosphine synthesis tellurides |
| CN108892112A (en) * | 2017-08-23 | 2018-11-27 | 苏州星烁纳米科技有限公司 | The nanocrystalline preparation method of metal selenide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583262A (en) * | 2012-01-04 | 2012-07-18 | 吉林大学 | Method for preparing oil soluble semiconductor nanocrystalline without phosphine |
| CN102676162A (en) * | 2012-05-04 | 2012-09-19 | 天津大学 | Preparation method for quaternary ZnCuInS3 quantum dot with high fluorescence |
| CN104445098A (en) * | 2014-12-16 | 2015-03-25 | 中国工程物理研究院化工材料研究所 | AgInSe2 nanocrystalline and preparation method thereof |
| CN105174235A (en) * | 2015-08-24 | 2015-12-23 | 中国科学技术大学 | Liquid-phase preparation method of cubic phase Cu2SnTe3 nanometer crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583262A (en) * | 2012-01-04 | 2012-07-18 | 吉林大学 | Method for preparing oil soluble semiconductor nanocrystalline without phosphine |
| CN102676162A (en) * | 2012-05-04 | 2012-09-19 | 天津大学 | Preparation method for quaternary ZnCuInS3 quantum dot with high fluorescence |
| CN104445098A (en) * | 2014-12-16 | 2015-03-25 | 中国工程物理研究院化工材料研究所 | AgInSe2 nanocrystalline and preparation method thereof |
| CN105174235A (en) * | 2015-08-24 | 2015-12-23 | 中国科学技术大学 | Liquid-phase preparation method of cubic phase Cu2SnTe3 nanometer crystal |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416777A (en) * | 2017-07-31 | 2017-12-01 | 吉林大学 | A kind of nanocrystalline method of no phosphine synthesis tellurides |
| CN107416777B (en) * | 2017-07-31 | 2019-11-22 | 吉林大学 | A method of no phosphine synthesis tellurides is nanocrystalline |
| CN108892112A (en) * | 2017-08-23 | 2018-11-27 | 苏州星烁纳米科技有限公司 | The nanocrystalline preparation method of metal selenide |
| CN108892112B (en) * | 2017-08-23 | 2022-07-29 | 苏州星烁纳米科技有限公司 | Preparation method of metal selenide nanocrystal |
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