CN111072059A - Cuboid-shaped CuInS2Efficient preparation method of/ZnS semiconductor nanocrystalline - Google Patents

Cuboid-shaped CuInS2Efficient preparation method of/ZnS semiconductor nanocrystalline Download PDF

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CN111072059A
CN111072059A CN201911419461.1A CN201911419461A CN111072059A CN 111072059 A CN111072059 A CN 111072059A CN 201911419461 A CN201911419461 A CN 201911419461A CN 111072059 A CN111072059 A CN 111072059A
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黄博
张辉朝
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Shanghai Sunpump Photoelectric Technology Co ltd
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Hangzhou Dianzi University
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Abstract

The invention discloses a cuboid-shaped CuInS2A high-efficiency preparation method of/ZnS semiconductor nanocrystalline. The method specifically comprises the following steps: (1) preparation of CuInS2the/ZnS nano core is dissolved in tri-n-octylphosphine after being purified to obtain TOP/NCs solution; (2) under the argon atmosphere, mixing sulfur powder with TOP, and carrying out ultrasonic treatment until clear TOP/S solution is obtained; (3) heating tri-n-octyl oxyphosphorus, zinc oxide and oleic acid to 120-130 ℃ in an argon environment for reacting for 50-60 minutes, and then heating to 345-350 ℃ to enable reactants to become clear solution; (4) injecting TOP/NCs solution into the product in the step (3), setting the temperature to be 335-340 ℃, injecting TOP/S solution when the temperature is restored to 335-340 ℃, and carrying out reverse reactionCooling to room temperature after 15-18 minutes to obtain cuboid-shaped CuInS2a/ZnS nanocrystal.

Description

Cuboid-shaped CuInS2Efficient preparation method of/ZnS semiconductor nanocrystalline
Technical Field
The invention relates to a high-efficiency preparation method of cuboid-shaped CuInS2/ZnS semiconductor nanocrystals.
Background
The development of new materials is the main driving force for the development of technology. The preparation and manipulation of nanocrystals and the recognition of their size and shape dependent properties have made great progress over the last two decades. Sodium (A)The performance of the rice material can be adjusted according to the chemical components and the geometric parameters. For example, the band gap of a semiconductor nanocrystal depends on the size of the nanocrystal. Therefore, by controlling the size of the nanocrystals in the nanoscale range, we can conveniently manipulate the optical properties of the material. This can be achieved by a wet chemical synthesis method, which generally produces a nanocrystalline colloidal solution with a shell protection of the organic ligand. The composition, size and shape of the resulting nanocrystals can be fine-tuned by adjusting the parameters of the synthesis, such as temperature, concentration and properties of the precursors and solvents. Especially for binary semiconductor materials (e.g., II-VI or IV-VI semiconductors), a number of synthesis schemes have been developed to achieve precise size and shape control. Cadmium-based nanocrystals (such as CdSe) have excellent and precisely controllable optical properties, enabling the development of commercial displays with high color gamut. However, the best studied II-VI and IV-VI semiconductor nanocrystals typically contain the highly toxic heavy metals cadmium and lead, which severely limits their large-scale production and use. While less toxic materials with similar optical properties, such as copper indium sulfide (CuInS), can be found in ternary I-III-VI semiconductors2)。CuInS2The nano crystal is a direct band gap semiconductor material, has high extinction coefficient and obvious defect tolerance in a visible spectrum range, and can be widely applied to the aspects of solar energy conversion, photoelectric detection, luminescent devices, photocatalysis, biomedicine and the like as a substitute material of toxic nano crystal. Thus, based on CuInS2The preparation and the shape control of the nanocrystalline are very important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides CuInS2A high-efficiency preparation method of/ZnS semiconductor nanocrystalline. The method can obtain cuboid CuInS in a short time2a/ZnS semiconductor nanocrystal.
In order to achieve the purpose, the technical scheme adopted by the invention is that the CuInS is cuboid-shaped2The efficient preparation method of the/ZnS semiconductor nanocrystal comprises the following steps:
step (1) of preparing CuInS2the/ZnS nano core is dissolved in tri-n-octylphosphine after being purified to obtain TOP/NCs solution; preferably, the average size of the nano-cores is 2.7nm, and the concentration is 45 nmol/mL;
step (2), mixing sulfur powder and TOP under an argon environment, and carrying out ultrasonic treatment until a clear TOP/S solution is obtained;
the concentration of sulfur in the TOP/S solution is 2.7-4.9 mol/L;
heating tri-n-octyl oxyphosphorus, zinc oxide and oleic acid to 120-130 ℃ in an argon environment for reacting for 50-60 minutes, and then heating to 345-350 ℃ to enable reactants to become clear solution;
the mass ratio of ZnO, oleic acid and tri-n-octyloxyphosphorus is 1: 5-5.1: 3-6.4;
step (4) injecting the TOP/NCs solution in the step (1) into the product in the step (3), setting the temperature to be 335-340 ℃, injecting the TOP/S solution in the step (2) when the temperature is restored to 335-340 ℃, reacting for 15-18 minutes, and cooling to room temperature to obtain cuboid-shaped CuInS2a/ZnS nanocrystal;
the ratio of the ZnO, the sulfur powder and the nano-core is 1: 3-3.1: 2.7 × 10-5～5.6×10-5。
Preferably, in the step (1), CuInS2The average grain diameter of the/ZnS nano core is 2.5-3.5 nm.
Preferably, in step (3), the mass ratio of ZnO to oleic acid is 1: 5.
Preferably, in the step (4), the temperature is set to 340 ℃ and the ratio of the amounts of ZnO to sulfur powder is 1: 3.
The technical scheme has the following beneficial effects:
compared with CuInS coated by the traditional method2The method can rapidly improve the thickness of the ZnS shell layer of the environment-friendly material to prepare the large-size nanocrystal, greatly enhances the stability of the nanocrystal, and the obtained nanocrystal has a cuboid shape and has potential application value in the aspect of ultraviolet photoelectric conversion.
Drawings
FIG. 1 shows the resulting CuInS2Transmission electron microscopy images of/ZnS nanocore.
FIG. 2 shows the resulting CuInS2Transmission electron microscopy images of/ZnS nanocrystals.
Fig. 3 is an absorption spectrum of the sample of fig. 1 and 2.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the following applicant will make further detailed descriptions of the present invention with reference to specific embodiments and the accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and those equivalents may fall within the scope of the present invention defined by the appended claims.
Implementation mode one
(1) Preparation of CuInS with an average size of 2.7nm2purifying/ZnS nano-core (NCs), dissolving in TOP to obtain TOP/NCs solution with nano-core concentration of 45nmol/mL, and FIG. 1 shows the obtained CuInS2Transmission electron microscopy of/ZnS nanonuclei, dashed line in FIG. 3 for the resulting CuInS2Absorption spectrum of/ZnS nano-core;
(2) under the argon atmosphere, mixing sulfur powder with TOP, and carrying out ultrasonic treatment until clear TOP/S solution is obtained; the concentration of sulfur in the TOP/S solution is 3 mol/L;
(3) taking 10mmol of tri-n-octyloxyphosphorus, adding 2mmol of ZnO and 10mmol of oleic acid, heating to 130 ℃ under the argon environment for reaction for 60 minutes, and then heating to 350 ℃ to enable reactants to become clear solution;
(4) injecting 2mL of TOP/NCs solution in the step (1) into the product in the step (3), setting the temperature to be 340 ℃, injecting 2mL of TOP/S solution in the step (2) when the temperature is recovered to 340 ℃, reacting for 18 minutes, and cooling to room temperature to obtain cuboid-shaped CuInS2The solid lines in fig. 2 and fig. 3 are the transmission electron microscopy image and the absorption spectrum, respectively, of the/ZnS nanocrystal.
Second embodiment
(1) Preparation of CuInS with an average size of 2.5nm2the/ZnS nano-cores (NCs) are dissolved in TOP after purification to obtain TOP/NCs solution, and the concentration of the nano-cores in the TOP/NCs solution is 52.6 nmol/mL;
(2) under the argon atmosphere, mixing sulfur powder with TOP, and carrying out ultrasonic treatment until clear TOP/S solution is obtained; the concentration of sulfur in the TOP/S solution is 2.7 mol/L;
(3) taking 9.1mmol of tri-n-octyloxyphosphorus, adding 1.8mmol of ZnO and 9mmol of oleic acid, heating to 120 ℃ in an argon environment for reaction for 50 minutes, and then heating to 345 ℃ to enable reactants to become clear solution;
(4) injecting 1.5mL of TOP/NCs solution in the step (1) into the product in the step (3), setting the temperature to be 335 ℃, injecting 2.1mL of TOP/S solution in the step (2) when the temperature is restored to 335 ℃, reacting for 15 minutes, and cooling to room temperature to obtain cuboid-shaped CuInS2a/ZnS nanocrystal.
Third embodiment
(1) Preparation of CuInS with an average size of 3.5nm2Purifying and dissolving/ZnS Nano Cores (NCs) in TOP to obtain a TOP/NCs solution, wherein the concentration of the nano cores in the TOP/NCs solution is 40 nmol/mL;
(2) under the argon atmosphere, mixing sulfur powder with TOP, and carrying out ultrasonic treatment until clear TOP/S solution is obtained; the concentration of sulfur in the TOP/S solution is 4.9 mol/L;
(3) taking 11.6mmol of tri-n-octyloxyphosphorus, adding 3mmol of ZnO and 15.3mmol of oleic acid, heating to 125 ℃ in an argon environment for reaction for 55 minutes, and then heating to 348 ℃ to change reactants into a clear solution;
(4) injecting 2.5mL of TOP/NCs solution in the step (1) into the product in the step (3), setting the temperature to be 3370 ℃, injecting 1.9mL of TOP/S solution in the step (2) when the temperature is recovered to 337 ℃, reacting for 16 minutes, and cooling to room temperature to obtain cuboid-shaped CuInS2a/ZnS nanocrystal.

Claims (4)

1. Cuboid-shaped CuInS2The efficient preparation method of the/ZnS semiconductor nanocrystal is characterized by comprising the following steps of:
(1) preparation of CuInS2purifying/ZnS nano-core NCs, dissolving in tri-n-octyl phosphorus TOP to obtain TOP/NCs solution, nano-core NCs in TOP/NCs solutionThe concentration of the core is 40.0-52.6 nmol/mL;
(2) under the argon atmosphere, mixing sulfur powder S with TOP, and carrying out ultrasonic treatment until a clear TOP/S solution is obtained, wherein the sulfur concentration in the TOP/S solution is 2.7-4.9 mol/L;
(3) heating tri-n-octyl oxyphosphorus, zinc oxide ZnO and oleic acid to 120-130 ℃ in an argon environment for reacting for 50-60 minutes, and then heating to 345-350 ℃ to change reactants into clear solution, wherein the mass ratio of the ZnO, the oleic acid and the tri-n-octyl oxyphosphorus is 1: 5-5.1: 3-6.4;
(4) injecting the TOP/NCs solution in the step (1) into the product in the step (3), setting the temperature to be 335-340 ℃, injecting the TOP/S solution in the step (2) when the temperature is restored to 335-340 ℃, reacting for 15-18 minutes, and cooling to room temperature to obtain cuboid-shaped CuInS2The amount ratio of ZnO, sulfur powder and nano-core is 1: 3-3.1: 2.7 × 10-5～5.6×10-5。
2. A cuboid shaped CuInS according to claim 12The efficient preparation method of the/ZnS semiconductor nanocrystal is characterized in that in the step (1), CuInS2The average grain diameter of the/ZnS nano core is 2.5-3.5 nm.
3. A cuboid shaped CuInS according to claim 12The efficient preparation method of the/ZnS semiconductor nanocrystal is characterized in that in the step (3), the mass ratio of ZnO to oleic acid is 1: 5.
4. A cuboid shaped CuInS according to claim 12The efficient preparation method of the/ZnS semiconductor nanocrystal is characterized in that in the step (4), the temperature is set to be 340 ℃, and the mass ratio of ZnO to sulfur powder is 1: 3.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2022082944A1 (en) * 2020-10-21 2022-04-28 南京晓庄学院 Optimization method for sulfide nanocrystals, and sn-s-co nanocrystals and optimization product of sn-s-co nanocrystals

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CN105369358A (en) * 2015-11-04 2016-03-02 北京理工大学 Method for performing ligand exchange on surface of semiconductor nanocrystalline material
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Publication number Priority date Publication date Assignee Title
WO2022082944A1 (en) * 2020-10-21 2022-04-28 南京晓庄学院 Optimization method for sulfide nanocrystals, and sn-s-co nanocrystals and optimization product of sn-s-co nanocrystals

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