CN106635022B - A method of the realization of sulfur family oxide is dissolved by alkyl hydrosulfide and prepares selenium or tellurides as semiconductor quantum dot without phosphine - Google Patents
A method of the realization of sulfur family oxide is dissolved by alkyl hydrosulfide and prepares selenium or tellurides as semiconductor quantum dot without phosphine Download PDFInfo
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Abstract
The invention belongs to fluorescence quantum preparation technical fields, more particularly to a kind of method that no phosphine prepares oil-soluble selenium or tellurides as semiconductor quantum dot, selenium or tellurium presoma are prepared more particularly to a kind of method of reduction of dissolved in alkyl hydrosulfide using selenium dioxide or tellurium dioxide as raw material, and utilizes the method for this precursor preparation high quality functionality selenium or tellurides as semiconductor quantum dot.Core of the invention content is that the dioxide of dissolved selenium or tellurium is removed with alkyl hydrosulfide, obtains the solution of selenium or tellurium.The dioxide of alkyl hydrosulfide and selenium or tellurium used in the present invention is common stable compound, and cheap, environmentally protective.Prepared presoma activity is high, can be compared with preparation several functions selenium or telluride quantum dots under temperate condition.It can effectively reduce preparation cost using the method, while reducing environmental pollution, the industrialized production and relevant LED industry to selenium or telluride quantum dots are significant.
Description
Technical field
The invention belongs to fluorescence quantum preparation technical fields, and in particular to a kind of no phosphine prepares oil-soluble selenium or tellurides
The method of semiconductor-quantum-point restores in alkyl hydrosulfide more particularly to one kind using selenium dioxide or tellurium dioxide as raw material molten
The method of solution prepares selenium or tellurium presoma, and utilizes this precursor preparation high quality functionality selenium or tellurides as semiconductor quantum dot
Method.
Background technique
Fluorescence selenium or tellurides as semiconductor quantum dot have narrow fluorescence emission spectrum, extensive colour gamut and good reason
Change stability, the Novel LED light source based on such quantum dot has become most competitive one of the technology of illumination display field.
Demand with people to selenium or tellurides as semiconductor quantum dot increasingly increases, the green batch of selenium or tellurides as semiconductor quantum dot
Amount production becomes a urgent problem to be solved.Currently, development is most mature and most classic prepares selenium or tellurides as semiconductor
The method of quantum dot surely belongs to hot injection method.Hot injection method is used and is rapidly injected in hot conditions into metal front liquid solution
The operating technology of nonmetallic presoma.This method growth mechanism is clear, can be effectively by the nucleation and growth mistake of quantum dot
Journey separates, to guarantee that the size uniformity of quantum dot, performance are stablized.In operation, a crucial step be prepare it is non-
Metal (selenium or tellurium) presoma.Mainly selenium powder, tellurium powder are dissolved using organic phosphines such as tributylphosphine, tri octyl phosphines, then will
It is injected into the source metal solution of high temperature.But these organic phosphonate reagents are not only harmful to human body, and pollute environment, and price
It is expensive.In addition, organic phosphonate reagent is easily oxidized air-sensitive, thus whole preparation process require in glove box into
Row, these all considerably increase the difficulty and cost that prepare quantum dot, limit the industrial applications of this preparation method.With
People constantly study, a series of no phosphines prepare selenium or the method for tellurides as semiconductor quantum dot is developed.Such as
Selenium powder is dissolved by heating in advance in high boiling ligand solvent or non-coordinating solvent, prepares selenide quantum dots.This method is wanted
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 are not particularly suited for the preparation of telluride quantum dots.In addition, in aqueous solution preparing cadmium selenide, cadmium telluride
Method is also developed.This method mainly utilizes sodium borohydride reduction selenium powder, tellurium powder, first prepares selenium in aqueous solution
Sodium hydride, sodium hydrogen telluride solution, further using the sodium hydrogen selenide of preparation, sodium hydrogen telluride as non-metal source, addition is ready to
The presoma of aqueous solution containing cadmium in, prepare cadmium selenide, cadmium telluride quantum dot by being heated to reflux.Although this improvement has eliminated
Machine phosphonate reagent, but since the boiling point of water is lower, reaction temperature is limited, it usually needs longer return time completes reaction.
It is unfavorable for the industrialized production of quantum dot.In addition, this method exists compared with big limitation, be only applicable to prepare selenium containing cadmium and mercury or
Tellurides as semiconductor quantum dot.Therefore, development simultaneously suitable for selenium or tellurides as semiconductor quantum dot it is easy, efficient, environmentally friendly,
Low cost, can industrialized production synthetic method it is extremely urgent.
Summary of the invention
The object of the invention is to prepare the selenium or tellurium presoma without phosphine of a kind of cheap and simple, and utilize this forerunner's system
Standby oil-soluble selenium or tellurides as semiconductor quantum dot, i.e., using selenium dioxide or tellurium dioxide as raw material, by it in alkyl hydrosulfide
Reduction of dissolved to obtain selenium or tellurium presoma, and utilizes this precursor preparation selenium or tellurides as semiconductor quantum dot.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 selects selenium dioxide or tellurium dioxide is raw material, and alkyl hydrosulfide is reducing agent and ligand solvent.Wherein, institute
The reaction reagent being related to is cheap, it is environmental-friendly, can be stabilized in air；Prepare selenium or tellurium presoma process without
The glove box operation of stringent anhydrous and oxygen-free is needed, risk is small；Prepared presoma activity height is, it can be achieved that compared under temperate condition
Quantum dot preparation is rapidly completed；Product quantum dot is functional, and has preferable experimental repeatability.Therefore, this method
It effectively reduces 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 to 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 are 0.1~1mol/L；
(3) under nitrogen protection, source metal (one or more of cadmium source, lead source, mercury source, Yin Yuan, copper source) is added
To in the mixed solution of aliphatic amine or fatty acid and 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 warming up to, the selenium of preceding step preparation or tellurium presoma are added, dioxy
The molar ratio for changing selenium or tellurium dioxide and source metal is 1:1~1:10, and the reaction was continued 5~30 minutes, obtains selenium or tellurides half
Conductor quantum dot.
The method of the invention can be used for preparing CdSe, CdTe, PbTe, HgTe, Ag2Te、Cu2The various selenium such as Te or telluride
Object semiconductor-quantum-point.
Cadmium source used in the above method 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..Rouge
Fat acid can be oleic acid, stearic acid, tetradecylic acid etc..
Detailed description of the invention
Fig. 1 (a): the transmission electron microscope photo of oil-soluble CdSe quantum dot prepared by embodiment 1, gained quantum dot size are equal
Even, monodispersity is good, average-size 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 light
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 are cubic-crystal；
Fig. 2 (a): the transmission electron microscope photo of oil-soluble CdTe quantum prepared by embodiment 3, gained quantum dot size are equal
Even, monodispersity is good, average-size 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 have 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 are equal
Even, monodispersity is good, average-size 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 have 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 are equal
Even, monodispersity is good, average-size 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 have 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 are equal
Even, monodispersity is good, average-size 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 have very narrow UV absorption and fluorescent emission half-peak breadth；
Fig. 6 (a): the transmission electron microscope photo of oil-soluble HgTe quantum dot prepared by embodiment 7, gained quantum dot size are equal
Even, monodispersity is good, average-size 1.9nm；
Fig. 6 (b): the UV absorption spectrogram of oil-soluble HgTe quantum dot prepared by embodiment 7, gained quantum dot is in visible light
There is very strong absorption efficiency in region；
Fig. 6 (c): the XRD spectra of oil-soluble HgTe quantum dot prepared by embodiment 7, gained quantum dot are cubic-crystal；
Fig. 7 (a): the transmission electron microscope photo of oil-soluble PbTe quantum dot prepared by embodiment 9, gained quantum dot size are equal
Even, monodispersity is good, average-size 11.3nm；
Fig. 7 (b): the XRD spectra of oil-soluble PbTe quantum dot prepared by embodiment 9, gained quantum dot are cubic-crystal；
Fig. 7 (c): the UV absorption spectrogram of oil-soluble PbTe quantum dot prepared by embodiment 9, gained quantum dot is in visible light
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 dot, gained quantum dot size are equal
Even, monodispersity is good, average-size 4.3nm；
Fig. 8 (b): oil-soluble Cu prepared by embodiment 102The XRD spectra of Te quantum dot, gained quantum dot are hexagonal crystal shape；
Fig. 8 (c): oil-soluble Cu prepared by embodiment 102The UV absorption spectrogram of Te quantum dot, 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 dot, gained quantum dot size are equal
Even, monodispersity is good, average-size 6.2nm；
Fig. 9 (b): oil-soluble Ag prepared by embodiment 112The UV absorption spectrogram of Te quantum dot, 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 dot, gained quantum dot are monoclinic form.
Specific embodiment
Below 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 mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation 3 times.It is stirred at room temperature under nitrogen protection, to SeO2All dissolution obtains yellow solution to powder, which makees
Semiconductor-quantum-point is synthesized for selenides for selenium presoma.
By 0.27g (1mmol) Cd (AC)2·2H2O is added in 1mL oleic acid and 9mL octadecene mixed solution.Reaction system
It vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, until Cd (AC)2·
2H2O dissolution.Then in N2Solution is warming up to 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-point.
Embodiment 2
By 0.06g (0.5mmol) SeO2Powder is added in 5mL lauryl mercaptan, and system vacuumizes leads to after ten minutes
Enter nitrogen, repetitive operation 3 times.It is stirred at room temperature under nitrogen protection, to SeO2All dissolution obtains yellow solution to powder, the solution
Semiconductor-quantum-point is synthesized for selenides as selenium presoma.
By 0.14g (0.5mmol) Cd (AC)2·2H2O is added in 1mL oleic acid and 9mL octadecene mixed solution.Reactant
System vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, until Cd
(AC)2·2H2O dissolution.Then in N2Solution is warming up to 200 DEG C under gas shielded, selenium presoma prepared above is added,
200 DEG C the reaction was continued 30 minutes, obtains CdSe semiconductor-quantum-point.
Embodiment 3
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amine and 5mL octadecylene.Reactant
System vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, by CdCl2·
2H2O dissolution, 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-point with green-fluorescent emission.50mg had into green emission
CdTe quantum is added in 0.5mL acrylic type light-cured resin, is stirred evenly.Mixture, which is covered in launch wavelength, is
The GaInN chip (5mm × 5mm) of 365nm.After ultraviolet light solidification, can there must be the LED component of green emission.
Embodiment 4
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amine and 5mL octadecylene.Reactant
System vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, by CdCl2·
2H2O dissolution, obtains milky white solution.Then in N2Temperature is risen to 130 DEG C under gas shielded, tellurium presoma prepared above is infused
Enter, reaction 10min stops heating, as shown in figure 3, obtaining the CdTe semiconductor-quantum-point that there is yellow fluorescence to emit.By 50mg
CdTe quantum with yellow emission is added in 0.5mL acrylic type light-cured resin, is stirred evenly.Mixture is covered
In the GaInN chip (5mm × 5mm) that launch wavelength is 365nm.After ultraviolet light solidification, can there must be the LED component of yellow emission
Embodiment 5
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amine and 5mL octadecylene.Reactant
System vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, by CdCl2·
2H2O dissolution, obtains milky white solution.Then in N2Temperature is risen to 140 DEG C under gas shielded, tellurium presoma prepared above is infused
Enter, reaction 10min stops heating, as shown in figure 4, obtaining the CdTe semiconductor-quantum-point with fluorescent orange.
Embodiment 6
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.32g (1.4mmol) CdCl2·2H2O is added in the mixed solution of 5mL oleyl amine and 5mL octadecylene.Reactant
System vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, by CdCl2·
2H2O dissolution, obtains milky white solution.Then in N2Temperature is risen to 185 DEG C under gas shielded, tellurium presoma prepared above is infused
Enter, reaction 10min stops heating, as shown in figure 5, obtaining the CdTe semiconductor-quantum-point with red fluorescence.50mg is had
The CdTe quantum of red emission is added in 0.5mL acrylic type light-cured resin, is stirred evenly.Mixture is covered in hair
The GaInN chip (5mm × 5mm) of a length of 365nm of ejected wave.After ultraviolet light solidification, can there must be the LED component of red emission
Embodiment 7
The tool that will be prepared in the CdTe quantum and 50mg embodiment 6 with green emission prepared in 50mg embodiment 3
There is the CdTe quantum of red emission to be added in 0.5mL acrylic type light-cured resin, stirs evenly.Mixture is covered in
Launch wavelength is the GaInN blue chip (5mm × 5nm) of 450nm.Ultraviolet light solidification after, can based on three primary colours have it is white
Photoemissive LED component.
Embodiment 8
By 0.16g (1mmol) TeO2Powder is added in 2mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.272g (1mmol) HgCl2It is added in the mixed solution of 8mL oleyl amine and 2mL octadecylene.Reaction system is taken out true
Empty, logical nitrogen 3 times, every time 10 minutes.Then it is heated to 80 DEG C under vacuum conditions to react 30 minutes, by HgCl2Dissolution, obtains
Milky white solution.Then in N2Solution is warming up to 100 DEG C under gas shielded, Te presoma prepared above is injected, reaction
5min stops heating, as shown in fig. 6, obtaining HgTe semiconductor-quantum-point.
Embodiment 9
By 0.01g (0.05mmol) TeO2Powder is added in 1mL lauryl mercaptan, and system vacuumizes leads to after ten minutes
Enter nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to
Room temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.136g (0.5mmol) HgCl2It is added in the mixed solution of 8mL oleyl amine and 2mL octadecylene.Reaction system is taken out
Vacuum is led to nitrogen 3 times, every time 10 minutes.Then it is heated to 80 DEG C under vacuum conditions to react 30 minutes, by HgCl2Dissolution, obtains
To milky white solution.Then in N2Solution is warming up to 100 DEG C under gas shielded, Te presoma prepared above is injected, reaction
5min stops heating, obtains HgTe semiconductor-quantum-point.
Embodiment 10
By 0.16g (1mmol) TeO2Powder is added in 1mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.278g (1mmol) PbCl2It is added in the mixed solution of 3mL oleic acid, 3mL oleyl amine and 4mL octadecylene.Reaction
System vacuumizes, is nitrogen 3 times, every time 10 minutes logical.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, by PbCl2
Dissolution, obtains transparent colourless solution.Then in N2Solution is warming up to 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-point.
Embodiment 11
By 0.16g (1mmol) TeO2Powder is added in 1mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.19g (1.4mmol) CuCl2It is added in the mixed solution of 5mL oleyl amine and 5mL octadecylene.Reaction system is taken out
Vacuum is led to nitrogen 3 times, every time 10 minutes.Then it is heated to 100 DEG C under vacuum conditions to react 30 minutes, by CuCl2Dissolution.
Then in N2Temperature is risen to 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-point.
Embodiment 12
By 0.16g (1mmol) TeO2Powder is added in 1mL lauryl mercaptan, and system vacuumizes to be passed through after ten minutes
Nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to room
Temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.34g (2mmol) AgNO3It is added in the mixed solution of 8mL oleyl amine and 2mL octadecylene.Reaction system is taken out true
Empty, logical nitrogen 3 times, every time 10 minutes.Then solution is warming up to 180 DEG C under nitrogen protection, by tellurium forerunner prepared above
Body injection, reaction 20min stops heating, as shown in figure 9, obtaining Ag2Te semiconductor-quantum-point.
Embodiment 13
By 0.08g (0.5mmol) TeO2Powder is added in 5mL lauryl mercaptan, and system vacuumizes leads to after ten minutes
Enter nitrogen, repetitive operation is three times.100 DEG C of stirrings under nitrogen protection, to TeO2All dissolution obtains orange solution to powder, is down to
Room temperature.The solution is as tellurium presoma for synthesizing semiconductor-quantum-point.
By 0.17g (1mmol) AgNO3It is added in the mixed solution of 8mL oleyl amine and 2mL octadecylene.Reaction system is taken out true
Empty, logical nitrogen 3 times, every time 10 minutes.Then solution is warming up to 180 DEG C under nitrogen protection, by tellurium forerunner prepared above
Body injection, reaction 10min stop heating, obtain Ag2Te semiconductor-quantum-point.
Claims (4)
1. a kind of dissolve the method that the realization of sulfur family oxide prepares selenium or tellurides as semiconductor quantum dot without phosphine by alkyl hydrosulfide,
Its step are as follows:
(1) under nitrogen protection, selenium dioxide is added to 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 are 0.1~1mol/L；
(3) under nitrogen protection, source metal is added in the mixed solution of fatty acid and octadecylene, the concentration of source metal is
0.1~0.5mol/L, 60~80 DEG C of heating stirrings dissolve source metal；Then 90~200 DEG C are warming up to, by step (1) or step
Suddenly the molar ratio of the selenium of (2) preparation or the addition of tellurium presoma, selenium dioxide or tellurium dioxide and source metal is 1:1~1:10, after
Continuous reaction 5~30 minutes, obtains selenium or tellurides as semiconductor quantum dot；
The alkyl hydrosulfide is spicy thioalcohol, lauryl mercaptan, hexadecyl mercaptan or Stearyl mercaptan；The fatty acid is
Oleic acid, stearic acid or tetradecylic acid.
2. a kind of realized by alkyl hydrosulfide dissolution sulfur family oxide as described in claim 1 prepares selenium or tellurides half without phosphine
The method of conductor quantum dot, it is characterised in that: obtain CdSe, CdTe, PbTe, HgTe, Ag2Te or Cu2Te semiconductor-quantum-point.
3. a kind of realized by alkyl hydrosulfide dissolution sulfur family oxide as described in claim 1 prepares selenium or tellurides half without phosphine
The method of conductor quantum dot, it is characterised in that: source metal is one or more of cadmium source, lead source, mercury source, Yin Yuan, copper source.
4. a kind of realized by alkyl hydrosulfide dissolution sulfur family oxide as claimed in claim 3 prepares selenium or tellurides half without phosphine
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。
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| 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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| 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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