Self-passivating quantum dot and preparation method thereof

Abstract

The invention relates to a self-passivating quantum dot and a preparation method thereof. The quantum dot is doped with a self-passivating element M and the self-passivating element M ranges from 0.1 wt % to 40 wt % in content. The self-passivating element M is selected from the group consisting of Al, Zr, Fe, Ti, Cr, Ta, Si, and Ni. The preparation method comprises the steps of: adding a quantum dot core and a solvent into a reaction vessel, controlling the temperature to be 100-120 C. and vacuumizing the reaction vessel for 30-50 min; filling the reaction vessel with inert gas, and rising the temperature to 230-280 C.; and injecting a coating material precursor solution into the reaction vessel for coating the quantum dot core according to the injection amount being 1 or 2 times by molar concentration of the quantum dot core element to prepare the self-passivating quantum dot.

Claims

1. A method of producing a self-passivating quantum dot, comprising: (1) adding an M precursor comprising a self-passivating element M to a quantum dot core precursor solution to form a quantum dot core doped with M; adding the quantum dot core doped with M and a solvent to a reaction vessel at 100-120 C., and vacuumizing the reaction vessel for 30-50 minutes; (2) filling the reaction vessel with inert gas, and rising the temperature to 230-280 C.; (3) injecting a coating material precursor solution into the reaction vessel for reaction to produce a self-passivating quantum dot with one layer of coating material, wherein the molar ratio of the coating material precursor solution to the quantum dot core is 1:1 or 2:1; and (4) when a coating layer is multilayer, repeating step (3) to continually form the coating material outside of the self-passivating quantum dot prepared in step (3) to produce a self-passivating quantum dot with multilayer coating material; wherein the self-passivating element M is selected from the group consisting of Al, Zr, Fe, Ti, Cr, Ta, Ni and Si.

2. The method of claim 1, wherein the self-passivating element M ranges from 0.1-40 wt % based on the self-passivating quantum dot prepared in step (3) or (4).

3. The method of claim 1, wherein the M precursor is selected from the group consisting of M chloride, M bromide, M fluoride, M nitrate, M sulfate, M perchlorate, M phosphate, M acetate, M formate, M oxalate, M propionate, trimethyl M, triethyl M, tripropyl M, triisopropyl M, tributyl M, tri-sec-butyl M, tri-tert-butyl M, tetraisopropyl M, M isopropoxide, M sec-butoxide or M acetylacetonate.

4. The method of claim 3, wherein the M precursor is M isopropoxide or M acetylacetonate.

5. The method of claim 1, wherein the coating material is the same as or different from a material of the quantum dot core.

6. The method of claim 1, wherein a coating layer outside of the quantum dot core comprises 1-20 layers of the coating material.

7. The method of claim 1, wherein the quantum dot core is a binary structure quantum dot core, a ternary quantum dot core or a quaternary structure quantum dot core.

8. The method of claim 7, wherein the binary structure quantum dot core is A.sub.mX.sub.q, the ternary structure quantum dot core is A.sub.mA.sub.nX.sub.q, the quaternary structure quantum dot core is A.sub.mA.sub.nA.sub.pX.sub.q; wherein each m, n, p and q are independently integers that are equal to or greater than 1; each A, A and A are independently selected from one of cadmium, zinc, mercury, lead, tin, gallium, indium, calcium, barium and copper, and A, A and A are different from each other; and X is selected from the group consisting of sulfur, selenium, phosphorus, arsenic, tellurium and antimony.

9. The method of claim 1, wherein the coating material is selected from the group consisting of admium selenide (CdSe), zinc selenide (ZnSe), mercury selenide (HgSe), cadmium sulfide (CdS), zinc sulfide (ZnS), mercury sulfide (HgS), cadmium telluride (CdTe), zinc telluride (ZnTe), mercury telluride (HgTe), gallium nitride (GaN), indium nitride (InN), gallium phosphide (GaP), gallium antimonide (GaSb), indium gallium phosphide (InGaP), zinc cadmium selenide (ZnCdSe) and cadmium zinc sulfide (CdZnS).

10. A method of producing a self-passivating quantum dot, comprising: (1) adding a quantum dot core and a solvent to a reaction vessel at 100-120 C., and vacuumizing the reaction vessel for 30-50 minutes; (2) filling the reaction vessel with inert gas, and rising the temperature to 230-280 C.; (3) injecting a coating material precursor solution doped with an M precursor comprising a self-passivating element M into the reaction vessel for reaction to produce a self-passivating quantum dot with one layer of coating material, wherein the molar ratio of the coating material precursor solution to the quantum dot core is 1:1 or 2:1; and (4) when a coating layer is multilayer, repeating step (3) to continually form the coating material outside of the self-passivating quantum dot prepared in step (3) to produce a self-passivating quantum dot with multilayer coating material; wherein the self-passivating element M is selected from the group consisting of Al, Zr, Fe, Ti, Cr, Ta, Ni and Si.

11. The method of claim 10, wherein the self-passivating element M ranges from 0.1-40 wt % based on the self-passivating quantum dot prepared in step (3) or (4).

12. The method of claim 10, wherein the M precursor is selected from the group consisting of M chloride, M bromide, M fluoride, M nitrate, M sulfate, M perchlorate, M phosphate, M acetate, M formate, M oxalate, M propionate, trimethyl M, triethyl M, tripropyl M, triisopropyl M, tributyl M, tri-sec-butyl M, tri-tert-butyl M, tetraisopropyl M, M isopropoxide, M sec-butoxide or M acetylacetonate.

13. The method of claim 10, wherein the quantum dot core is a binary structure quantum dot core, a ternary quantum dot core or a quaternary structure quantum dot core.

14. The method of claim 13, wherein the binary structure quantum dot core is A.sub.mX.sub.q, the ternary structure quantum dot core is A.sub.mA.sub.nX.sub.q, the quaternary structure quantum dot core is A.sub.mA.sub.nA.sub.pX.sub.q; wherein each m, n, p and q are independently integers that are equal to or greater than 1; each A, A and A are independently selected from one of cadmium, zinc, mercury, lead, tin, gallium, indium, calcium, barium and copper, and A, A and A are different from each other; and X is selected from the group consisting of sulfur, selenium, phosphorus, arsenic, tellurium and antimony.

15. The method of claim 10, wherein the coating material is selected from the group consisting of admium selenide (CdSe), zinc selenide (ZnSe), mercury selenide (HgSe), cadmium sulfide (CdS), zinc sulfide (ZnS), mercury sulfide (HgS), cadmium telluride (CdTe), zinc telluride (ZnTe), mercury telluride (HgTe), gallium nitride (GaN), indium nitride (InN), gallium phosphide (GaP), gallium antimonide (GaSb), indium gallium phosphide (InGaP), zinc cadmium selenide (ZnCdSe) and cadmium zinc sulfide (CdZnS).

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is TEM picture of aluminum-doped core-shell structure quantum dot;

(2) FIG. 2 is TEM picture of aluminum-doped CIS(CuInS.sub.2)/ZnS core-shell structure quantum dot;

(3) FIG. 3 is fluorescence stability of aluminum-doped CdSe/CdS core-shell structure quantum dot;

(4) FIG. 4 is fluorescence stability of aluminum-doped CIS/ZnS core-shell structure quantum dot;

(5) FIG. 5 is fluorescence stability of peroxidating reagent processing chromium-doped CdSe/CdS core-shell structure quantum dot;

(6) FIG. 6 is fluorescence stability of peroxidating reagent processing aluminum-doped CdSe/CdS core-shell structure quantum dot;

DETAILED DESCRIPTION OF THE INVENTION

(7) The preparation method of a self-passivating quantum dot, comprising the following steps:

(8) (1) adding a quantum dot core and a solvent into a reaction vessel, controlling the temperature to be 100-120 DEG C. and vacuumizing the reaction vessel for 30-50 min;

(9) (2) filling the reaction vessel with inert gas, and rising the temperature to 230-280 DEG C.;

(10) (3) adopting an injection reaction method, injecting a coating material precursor solution into the reaction vessel for coating the quantum dot core to prepare the self-passivating quantum dot, where the molar ratio of the coating material precursor solution to the quantum dot core is 1:1 or 2:1.

(11) If the quantum dot core is M-doped (M=A1, Zr, Fe, Ti, Cr, Ta, Si, Ni) or M-undoped, when the quantum dot core is coated, the coating material precursor solution contains or contains no M precursor, if the quantum dot core is M-undoped, the coating material precursor solution contains M precursor, so as to ensure M is doped in the quantum dot, and M ranges from 0.1 wt % to 40 wt % in content in the self-passivating quantum dot.

(12) The quantum dot core can be a binary structure quantum dot core, a ternary structure quantum dot core or a quaternary structure quantum dot core, wherein the binary structure quantum dot core is A.sub.mX.sub.q, wherein A is selected from a group consisting of cadmium, zinc, mercury, lead, tin, gallium, indium, calcium, barium or copper, and X is selected from a group consisting of sulfur, selenium, nitrogen, phosphorus, arsenic, tellurium and antimony; the ternary structure quantum dot core is A.sub.mA.sub.nX.sub.q, wherein each m, n and q are integers that are equal to or greater than 1; A and A are respectively one of cadmium, zinc, mercury, lead, tin, gallium, indium, calcium, barium or copper, A and A are different with each other, and X is selected from a group consisting of sulfur, selenium, nitrogen, phosphorus, arsenic, tellurium and antimony; the quaternary structure quantum dot core is A.sub.mA.sub.nA.sub.pX.sub.q, wherein each m, n, p and q are integers that are equal to or greater than 1; A, A and A are respectively one of cadmium, zinc, mercury, lead, tin, gallium, indium, calcium, barium or copper, A, A and A are different with each other, and X is selected from a group consisting of sulfur, selenium, phosphorus, arsenic, tellurium and antimony. The coating material is selected from the group consisting group II-VI, group II-V, group III-V, group IV-VI, group II-IV-V, and group II-IV-VI semiconductor material, comprising cadmium selenide (CdSe), zinc selenide (ZnSe), mercury selenide (HgSe), cadmium sulfide (CdS), zinc sulfide (ZnS), mercury sulfide (HgS), cadmium telluride (CdTe), zinc telluride (ZnTe), mercury telluride (HgTe), indium nitride (InN), gallium nitride (GaN), gallium phosphide (GaP), gallium antimonide (GaSb), indium gallium phosphide (InGaP), zinc cadmium selenide (ZnCdSe) and cadmium zinc sulfide (CdZnS). 2-20 layers outside of the quantum dot core are coated.

(13) For example if the quantum dot core is quantum dot CdSe, it can be obtained by high temperature injection method, comprising following steps:

(14) (1) mixing 16 mmol of cadmium oxide, 16 ml of oleic acid and 40 ml of octadecene into a reactor, and vacuumizing the reactor for 30-50 min under 100-120 DEG C.;

(15) (2) filling the reactor with nitrogen, rising the temperature to 280-300 DEG C., when the solution becomes clear, cooling to 270 DEG C.;

(16) (3) rapid injecting 8 mmol of trioctylphosphine-selenium solution into the reactor, cooling to 240 DEG C., reacting for 3-5 min, cleaning and obtaining CdSe quantum dot.

(17) If the self-passivating quantum dot core is doped with binary structure CdSe, it can be obtained by high temperature injection method, comprising following steps:

(18) (1) adding 16 mmol of cadmium oxide, 16 ml of oleic acid, 1.6 mmol of M isopropoxide and 40 ml of octadecene into a reactor, and vacuumizing the reactor for 30-50 min under 100-120 DEG C.;

(19) (2) filling the reactor with nitrogen, rising the temperature to 280-300 DEG C., when the solution becomes clear, cooling to 270 DEG C.;

(20) (3) rapid injecting 8 mmol of trioctylphosphine-selenium solution into the reactor, cooling to 240 DEG C., reacting for 3-5 min, cleaning and obtaining M-doped binary structure quantum dot CdSe.

(21) The present invention is described in detail with reference to embodiments and drawings.

Embodiment 1

(22) Preparation of Aluminum-Doped CdSe/CdS Core-Shell Structure Quantum Dot

(23) Preparation of CdSe core quantum dot: adding 16 mmol of cadmium oxide, 16 ml of oleic acid, 1.6 mmol of oleic acid and 40 ml of octadecene into a three-necked flask, vaccumizing the flask for 30 min under 120 DEG C., rising the temperature to 290 DEG C. in the atmosphere of nitrogen, when the solution becomes clear, cooling to 270 DEG C.; rapid injecting 8 mmol of tris(trimethylsilyl)phosphine-selenium solution into the three-necked flask, cooling to 240 DEG C. and reacting for 3 min. After the reaction is completed, cleaning the CdSe quantum dot and taking it as a core quantum dot stock solution.

(24) Adding 0.1 mmol of CdSe stock solution, 20 ml of octadecene into 100 ml of the three-necked flask, vaccumizing the flask for 30 min under 120 DEG C., rising the temperature to 280 DEG C. in the atmosphere of nitrogen; starting micro-injection pump under 230 DEG C., injecting aluminum and sulfur precursor solution and oleic acid cadmium solution into the flask, adjusting parameters of injection pump, so that the generated CdS is 2 times by molar weight of CdSe. In whole reaction, aluminum is injected by molar weight according to 0.5-2 times of Cd in CdS. FIG. 1 shows TEM picture of aluminum-doped CdSe/CdS core-shell quantum dot, as shown in the figure, the structure of prepared aluminum-doped CdSe/CdS core-shell quantum dot is regular close to a sphere, and the quantum dot size is distributed evenly.

Embodiment 2

(25) Preparation of Aluminum-Doped CIS/ZnS Core-Shell Structure Quantum Dot

(26) Preparation of CIS core quantum dot: placing 0.5032 mmol of cuprous iodide, 0.5497 mmol of indium acetate, 60 ml of N-dodecyl mercaptan, 40 ml of octadecene and 0.5 ml of oleylamine into 250 ml of three-necked flask. After filling nitrogen for 20 min, heating the temperature to 100 DEG C., keeping the temperature for 1 h until the solution in the flask becomes clear and transparent, rising the temperature to 230 DEG C. with rate of 13 DEG C./min, starting timing, stopping reaction after 1 h, cooling and taking it as core quantum dot stock solution.

(27) Adding 0.1 mmol of CIS stock solution, 20 ml of octadecene into 100 ml of the three-necked flask, vaccumizing the flask for 30 min under 120 DEG C. Starting micro-injection pump to 230 DEG C. in the atmosphere of nitrogen, injecting aluminum and sulfur precursor solution and oleic acid zinc solution into the flask, adjusting parameters of injection pump, so that the generated ZnS is 2 times by molar weight of CIS. In whole reaction, aluminum is injected by molar weight according to 0.5-2 times of Zn. FIG. 2 shows TEM picture of aluminum-doped CIS/ZnS core-shell quantum dot, as shown in the figure, the structure of prepared aluminum-doped CIS/ZnS core-shell quantum dot is regular, and the quantum dot size is distributed evenly

Embodiment 3

(28) Preparation of Cr-Doped InP/ZnS Core-Shell Structure Quantum Dot

(29) Preparation of InP core quantum dot: placing 0.2 mmol of indium acetate, 8 ml of octadecene, and 0.6 mmol of myristic acid into 100 ml of three-necked flask. After filling nitrogen for 20 min, heating the temperature to 100 DEG C., keeping the temperature for 1 h until the solution in the flask becomes clear and transparent, rising the temperature to 270 DEG C. with rate of 13 DEG C./min, rapid injecting 0.1 mmol of tris(trimethylsilyl)phosphine solution into the three-necked flask, cooling to 250 DEG C. and reacting for 20 min. After the reaction is completed, cleaning the indium phosphide quantum dot and taking it as a core quantum dot stock solution.

(30) Adding 0.1 mmol of InP core quantum dot stock solution, 20 ml of octadecene into 100 ml of three-necked flask, vaccumizing the flask for 30 min under 120 DEG C., starting micro-injection pump to 230 DEG C. in the atmosphere of nitrogen, injecting Cr and sulfur precursor solution and oleic acid zinc solution into the flask, adjusting parameters of injection pump, so that the generated ZnS is 2 times by molar weight of InP. In whole reaction, Cr is injected by molar weight according to 0.5-2 times of Zn. The structure of prepared Cr-doped InP/ZnS core-shell quantum dot is regular, and the quantum dot size is distributed evenly.

Embodiment 4

(31) Photostablity Test of Aluminum-Doped CdSe/CdS Core-Shell Structure Quantum Dot;

(32) Preparing 450 nm of CdSe/CdS quantum dot and aluminum-doped CdSe/CdS quantum dot toluene solution with 0.1 absorbance and the same coating layer, adding solution of same volume in sealed test bottle respectively, placing the bottle in blue light plane light source (450 nm, Philips) of 0.2 A and 50V (10 W, energy density is 0.35 W/cm.sup.2), taking out quantitive sample after a period of time, testing the fluorescence spectrum, integrating and obtaining corresponding fluorescence peak intergral area, and intensity-time decay curve is made by the comparison of the intergral area and initial fluorescence peak intergral area. FIG. 3 shows light decay curve of CdSe/CdS core-shell quantum dot under different molar ratio of aluminum and cadmium. As seen in the figure, compared with undoped CdSe/CdS quantum dot, the stability of aluminum-doped CdSe/CdS quantum dot is improved under different molar ratio of aluminum and cadmium, and when the molar ratio of aluminum and cadmium is 0.5:1, the stability of aluminum-doped CdSe/CdS quantum dot is the best.

Embodiment 5

(33) Photostablity Test of Aluminum-Doped CIS/ZnS Core-Shell Structure Quantum Dot;

(34) Preparing 450 nm of CIS/ZnS quantum dot and aluminum-doped CIS/ZnS quantum dot toluene solution with 0.1 absorbance and the same CIS coating layer, adding solution of same volume in sealed test bottle respectively, placing the bottle in blue light plane light source (450 nm, Philips) of 0.2 A and 50V (10 W, energy density is 0.35 W/cm.sup.2), taking out quantitive sample after a period of time, testing the fluorescence spectrum, integrating and obtaining corresponding fluorescence peak intergral area, and intensity-time decay curve is made by the comparison of the intergral area and initial fluorescence peak intergral area. FIG. 4 shows light decay curve of CIS/ZnS core-shell quantum dot under different molar ratio of aluminum and zinc. As seen in the figure, compared with undoped/ZnS quantum dot, the stability of CIS aluminum-doped CIS/ZnS quantum dot is improved under different molar ratio of aluminum and zinc, and when the molar ratio of aluminum and zinc is 0.5:1, the stability of aluminum-doped CIS/ZnS quantum dot is the best.

Embodiment 6

(35) Preparation of Fe-Doped CdSe/CdTe Core-Shell Structure Quantum Dot

(36) a. Preparation of Quantum Dot CdSe

(37) (1) mixing 16 mmol of cadmium oxide, 16 ml of oleic acid and 40 ml of octadecene into a reactor, and vacuumizing the reactor for 50 min under 100 DEG C.;

(38) (2) filling the reactor with nitrogen, rising the temperature to 280 DEG C., when the solution becomes clear, cooling to 270 DEG C.;

(39) (3) rapid injecting trioctylphosphine-selenium solution into the reactor, the molar ratio of the trioctylphosphine-selenium and the cadmium oxide is 1:2, cooling to 240 DEG C., reacting for 3 min, cleaning and obtaining CdSe quantum dot.

(40) b. Preparation of Fe-Doped CdSe/CdTe Core-Shell Structure Quantum Dot

(41) (1) adding binary structure quantum dot core CdSe and a solvent octadecene into a reaction vessel, controlling the temperature to be 100 DEG C. and vacuumizing the reaction vessel for 50 min;

(42) (2) filling the reaction vessel with inert gas, and increasing the temperature to 230 DEG C.;

(43) (3) adopting an injection reaction method, injecting a coating material precursor solution (including Fe precursor solution, Cd precursor solution and Te precursor solution) into the reaction vessel for coating the quantum dot core according to the injection amount being 1 times of the quantum dot core to prepare the self-passivating quantum dot.

(44) (4) adopting the same coating material precursor to repeat step (3) for 20 times, a layer of CdTe is coated again outside of the self-passivating quantum dot prepared in step (3), and obtaining two-layer coated Fe-doped CdSe/CdTe core-shell structure quantum dot, and Fe is 0.1 wt % in content.

Embodiment 7

(45) A. the self-passivating quantum dot core is doped with binary structure CdSe is obtained by high temperature injection method, comprising following steps:

(46) (1) adding 16 mmol of cadmium oxide, 16 ml of oleic acid, 1.6 mmol of M isopropoxide and 40 ml of octadecene into a reactor, and vacuumizing the reactor for 30 min under 120 DEG C. (M=A1, Zr, Fe, Ti, Cr, Ta, Si or Ni);

(47) (2) filling the reactor with nitrogen, rising the temperature to 300 DEG C., when the solution becomes clear, cooling to 270 DEG C.;

(48) (3) rapid injecting trioctylphosphine-selenium solution into the reactor, the molar ratio of the trioctylphosphine-selenium and the cadmium oxide is 1:2, cooling to 240 DEG C., reacting for 5 min, cleaning and obtaining aluminum-doped binary structure quantum dot core CdSe.

(49) b. The preparation method of a self-passivating quantum dot, comprising the following steps:

(50) (1) adding M-doped binary structure quantum dot core CdSe and a solvent octadecene into a reaction vessel, controlling the temperature to be 120 DEG C. and vacuumizing the reaction vessel for 30 min;

(51) (2) filling the reaction vessel with inert gas, and rising the temperature to 280 DEG C.;

(52) (3) adopting an injection reaction method, injecting a coating material precursor solution (including Zn precursor solution and S precursor solution) into the reaction vessel for coating the quantum dot core according to the injection amount being 2 times of the quantum dot core to obtain M-doped CdSe/ZnS core-shell structure quantum dot.

(53) (4) adopting different coating material precursor solution containing or containing no M precursor solution (M=Al, Zr, Fe, Ti, Cr, Ta, Si or Ni), 20 layers of coating material are sequentially coated outside of the M-doped CdSe/ZnS core-shell structure quantum dot, the doped M element in each layer of coating material is the same or different, and preparing the self-passivating quantum dot product, and in the product, aluminum is 40 wt % in content, the coating material precursor solution is soluable solution of element comprising coating material.

Embodiment 8

(54) (1) preparing benzoyl peroxide toluene solution with concentration of 0.05 mmol/mL;

(55) (2) adding 100 microliter of 0.05 mmol/mL benzoyl peroxide toluene solution into 2 ml of CdSe/CdS:Cr toluene solution, water bathing for 2 h under 60 DEG C., wherein the concentration of CdSe/CdS:Cr toluene solution is 15 mg/mL;

(56) (3) cleaning CdSe/CdS:Cr quantum dot solution for comparing stability.

Embodiment 9

(57) (1) spin coating CdSe/CdS:Cr toluene solution with concentration of toluene solution on silicon wafer;

(58) (2) putting the silicon wafer into the plasma generator for processing 0.5 h, and dissolving in the toluene solution for stability test.

(59) It should be emphasized that above disclosure are merely some embodiments, and are described for clear understanding the principle of the disclosure, many variations and modifications can be made to above embodiments without departing from the spirit and principle of the disclosure, and these variations and modifications shall be within the scope of the disclosure.