InSb quantum dot and preparation method and application thereof
InSb quantum dots are prepared by using indium nanocrystals and antimony nanocrystals to uniformly mix and heat up reaction in organic solvents, which solves the toxicity and treatment problems of precursor materials in the prior art, and achieves a cheap, simple preparation process and high-performance products.
Patent Information
- Application Number
- CN202411625083.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-14
- Publication Date
- 2025-02-25
AI Technical Summary
In the prior art, when preparing InSb quantum dots, the precursor materials are highly toxic, harsh in handling conditions, expensive, flammable and unstable, which affects the repetition and uniformity of the products and limits the development of materials and related optoelectronic applications.
InSb quantum dots were prepared by homogeneous mixing in organic solvents and heating reactions in the presence of ligands. This method is simple, the precursor is cheap and easy to obtain, and has the potential for large-scale application production.
The cost of preparing InSb quantum dots is reduced, and the obtained products have good crystalline form and infrared spectral absorption, which are suitable for high-performance electronic devices, infrared detectors and solar energy conversion fields.
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Figure CN119521926A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the field of nanotechnology science, and in particular to an InSb quantum dot and a preparation method and application thereof. Background Art
[0002] InSb in the III-V semiconductor group has low toxicity, a narrow band gap (0.17 eV), a large excitation Bohr radius (~60 nm), and a high charge mobility (~78000 cm 2 / (V s) 2 ), low exciton binding energy (0.5meV) and other excellent physical properties, and the absorption range of InSb colloidal quantum dots can be modulated from near infrared to mid-infrared (1-5μm). The above characteristics make solution-processable indium antimonide quantum dots have great application potential in high-performance electronic devices, infrared detectors and solar energy conversion.
[0003] Indium antimonide quantum dots themselves have strong covalent properties, and have higher requirements for synthesis conditions, requiring highly reactive precursors and high reaction temperatures. At present, the main methods for preparing InSb nanocrystals are organometallic vapor phase epitaxy, laser-assisted catalytic growth, and liquid phase methods. They each have their own characteristics, but they also have some limitations. For example, the above three preparation methods require relatively high reaction temperatures (organometallic vapor phase epitaxy: 400-700°C; laser-assisted catalytic growth: ~800°C; liquid phase method: 240-360°C). A Chinese patent document with publication number CN115726042A discloses an indium antimonide crystal and a preparation method thereof. Indium and antimony are charged into a single crystal furnace at a molar ratio of In:Sb=1.5-4:1; a hydrogen atmosphere is maintained in the single crystal furnace, the temperature is raised to 800-1000°C to melt the indium and antimony, and the temperature is kept for 12-36 hours; the temperature is lowered to a crystal growth temperature of 445-525°C, and the temperature is kept until the crystal completes growth, thereby obtaining an InSb crystal.
[0004] A Chinese patent document with publication number CN111244761A discloses a GaSb-based InSb quantum dot and a preparation method thereof, comprising the following steps: obtaining a GaSb substrate; placing the GaSb substrate in a molecular beam epitaxial growth chamber for deoxidation treatment; growing a GaSb buffer layer on the GaSb substrate; growing an AlAs nucleation layer on the GaSb buffer layer; and growing an InSb quantum dot layer on the AlAs nucleation layer, wherein the growth temperature of the InSb quantum dot layer is 380-480°C.
[0005] At present, the lack of suitable In and Sb precursors is the main bottleneck faced by the liquid phase synthesis of InSb quantum dots. At present, the synthesis of indium antimonide quantum dots usually uses precursors such as Sb[NMe2]3, In[N(SiMe3)2]3, SbH3 and Sb[N(SiMe3)2]3. Such precursors are highly toxic or have harsh processing conditions, are expensive, flammable and unstable, which greatly affects the repeatability and uniformity of the product, further restricting the development of indium antimonide quantum dot materials and related optoelectronic applications. Summary of the invention
[0006] The invention provides an InSb quantum dot and a preparation method thereof. The preparation method is simple, and its precursor is cheap and readily available, and has the potential for large-scale application and production.
[0007] The technical solution of the present invention is as follows:
[0008] A method for preparing InSb quantum dots comprises: dispersing indium nanocrystals and antimony nanocrystals in an organic solvent and mixing them uniformly; heating to 60-300° C. and reacting for 0.1-120 min in the presence of a ligand to obtain InSb quantum dots.
[0009] Preferably, in the mixed dispersion of indium nanocrystals and antimony nanocrystals, the concentrations of indium nanocrystals and antimony nanocrystals are independently 0.1-20 mg / mL.
[0010] Preferably, the preparation method of InSb quantum dots comprises: dispersing indium nanocrystals and antimony nanocrystals in an organic solvent and mixing them evenly, adding a ligand, heating to 60-300°C at a heating rate of 1-30°C / min, reacting for 0.1-120min, and obtaining InSb quantum dots.
[0011] Preferably, the ligand is at least one of tertiary alkyl phosphine, secondary alkyl phosphine, aromatic phosphine and fatty acid; the organic solvent is at least one of fatty amine and olefin; in the reaction system, the molar ratio of the ligand to indium nanocrystals or antimony nanocrystals is greater than 0.1.
[0012] Preferably, after the reaction is completed, a polar solvent is added to the reaction solution and centrifuged to obtain indium antimonide quantum dots.
[0013] The preparation method of indium nanocrystals is as follows: in an inert atmosphere at 40-300° C., reacting an indium precursor with a reducing agent and / or an organic base for 0.1-30 minutes to obtain indium nanocrystals;
[0014] The preparation method of antimony nanocrystals is as follows: in an inert atmosphere at 40-300° C., an antimony precursor reacts with a reducing agent and / or an organic base for 0.1-30 minutes to obtain antimony nanocrystals.
[0015] Preferably, the method for preparing indium nanocrystals comprises:
[0016] (1-1) dissolving an indium precursor in a mixture of toluene and aliphatic amine to form an indium precursor solution; the indium precursor concentration in the indium precursor solution is 0.1-1 mol / L;
[0017] (1-2) Under an inert atmosphere, the solvent is heated to a temperature of K1, an indium precursor solution is added, an organic base is added or not added, and the reaction is continued for T1 time, and then a reducing agent is added. The reaction is continued for T2 time, and then the reaction is cooled to obtain an indium nanocrystal precursor solution.
[0018] Preferably, the method for preparing antimony nanocrystals comprises:
[0019] (2-1) dissolving an antimony precursor in a mixture of toluene and aliphatic amine to form an antimony precursor solution; the concentration of indium precursor in the antimony precursor solution is 0.1-1 mol / L;
[0020] (2-2) Under an inert atmosphere, the solvent is heated to K2 temperature, an antimony precursor solution is added, an organic base is added or not added, and the reaction is continued for T3 time, and then a reducing agent is added. The reaction is continued for T4 time and then cooled to obtain an antimony nanocrystal precursor solution.
[0021] After mixing the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, adding the ligand, heating to 60-300° C. at a heating rate of 1-30° C. / min, reacting for 0.1-120 min, and obtaining InSb quantum dots.
[0022] In the mixed solution of the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, the concentration of the indium nanocrystal and the antimony nanocrystal is 0.1-20 mg / mL.
[0023] Preferably, the indium precursor is at least one of indium chloride, indium bromide, indium iodide, indium acetate, and indium fatty carboxylate.
[0024] Preferably, the antimony precursor is at least one of antimony chloride, antimony bromide, antimony iodide and tris(dimethylamino)antimony.
[0025] The solvent is a fatty amine and / or a long-chain olefin; the fatty amine is a straight-chain fatty amine and / or a branched-chain fatty amine; and the molar ratio of the fatty amine to toluene is greater than 0.01.
[0026] Furthermore, the fatty amine is oleylamine and / or octylamine.
[0027] The reducing agent is at least one of lithium triethylborohydride, sodium borohydride, diisobutylaluminum hydride, and N,N-dimethylethamine aldehyde alkane complex; and the organic base is an organic base with a pKa greater than 15.
[0028] Furthermore, the organic base is tert-butyl lithium and / or lithium diisopropylamide.
[0029] Preferably, the molar ratio of the reducing agent or organic base to indium in the indium precursor solution is greater than 1; and the molar ratio of the reducing agent or organic base to antimony in the antimony precursor solution is greater than 1.
[0030] Preferably, K1 temperature and K2 temperature are independently 40-300° C.; T1 time, T2 time, T3 time, and T4 time are independently 0-10 min.
[0031] When T1 time, T2 time, T3 time or T4 time is 0, it represents continuous feeding.
[0032] Further preferably, the K1 temperature and the K2 temperature are independently 100-200°C.
[0033] The present invention also provides InSb quantum dots prepared by the above preparation method.
[0034] The present invention also provides the use of the InSb quantum dots in preparing colloidal quantum dot infrared detectors, solar cells or light-emitting devices.
[0035] Compared with the prior art, the present invention has the following beneficial effects:
[0036] The invention uses antimony nanocrystals and indium nanocrystals as precursors to prepare indium antimonide quantum dots. The preparation method of the antimony nanocrystals and indium nanocrystals is simple, and the required initial raw materials are cheap and easily available, which reduces the cost of preparing indium antimonide quantum dots and is conducive to commercial production. The obtained indium antimonide quantum dots have good crystal form and infrared spectrum absorption, and can be applied to high-performance electronic devices, infrared detectors, solar energy conversion and other fields.
[0037] The preparation method of the present invention can adjust the size of InSb quantum dots in a wide range, the absorption wavelength can be made longer, and the prepared InSb quantum dots have better monodispersity and are more uniform, and the product does not need to be processed by complex size-selective precipitation technology. BRIEF DESCRIPTION OF THE DRAWINGS
[0038] Figure 1 This is a transmission electron microscope image of the indium antimonide quantum dots obtained in Example 1;
[0039] Figure 2 This is a transmission electron microscope image of the indium antimonide quantum dots obtained in Example 2;
[0040] Figure 3 This is a transmission electron microscope image of the indium antimonide quantum dots obtained in Example 3;
[0041] Figure 4 This is a transmission electron microscope image of the indium antimonide quantum dots obtained in Example 4;
[0042] Figure 5 This is a transmission electron microscope image of the indium antimonide quantum dots obtained in Example 5;
[0043] Figure 6 is the X-ray diffraction pattern of indium antimonide quantum dots obtained in Example 1;
[0044] Figure 7 The ultraviolet-visible-near-infrared absorption spectrum of indium antimonide quantum dots obtained in Example 1;
[0045] Figure 8 This is the photoelectric response diagram of indium antimonide quantum dots obtained in Example 6. DETAILED DESCRIPTION
[0046] The present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be pointed out that the embodiments described below are intended to facilitate the understanding of the present invention and do not have any limiting effect on the present invention.
[0047] Embodiment 1:
[0048] A method for preparing indium antimonide quantum dots comprises the following steps:
[0049] (1) 3.4 mL of toluene and 0.6 mL of oleylamine were mixed, 1.56 mmol of InCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M indium precursor solution.
[0050] (2) 3.4 mL of ethanol and 0.6 mL of oleylamine were mixed, 1.56 mmol of SbCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M antimony precursor solution.
[0051] (3) 1.5 ml of oleylamine was injected into a three-necked flask, and the temperature was raised to 160° C. and maintained for 5 min under inert atmosphere protection. 1.5 mL of 1 M lithium triethylborohydride n-octyl ether solution was injected, and the temperature was continued to be heated and stirred to stabilize at 160° C. 0.1 mL of indium precursor solution was rapidly injected into the above solution, wherein the molar ratio of lithium triethylborohydride to indium was 40, and after heating for 30 s, the reaction liquid was cooled to room temperature in an ice water bath to obtain an indium nanocrystal precursor solution.
[0052] (4) 1.5 mL of oleylamine was injected into a three-necked flask, and the temperature was raised to 160° C. and maintained for 5 min under an inert atmosphere. 0.4 mL of 2 M lithium diisopropylamide solution was injected, and the temperature was continued to be heated and stirred to stabilize at 160° C. 0.1 mL of antimony precursor solution was quickly injected into the above solution, wherein the ratio of lithium diisopropylamide to antimony was 20. After heating for 1 min, the reaction liquid was cooled to room temperature in an ice water bath to obtain an antimony nanocrystal precursor solution.
[0053] (5) After mixing the above-mentioned indium nanocrystal precursor solution and antimony nanocrystal precursor solution, the temperature was raised to 240° C. at 3° C. / min and maintained for 30 min to obtain an indium antimonide quantum dot mixed solution.
[0054] (6) 0.1 mL of oleic acid was added to the above mixture and stirred for 10 min. 8 mL of a mixture of methanol and toluene with a volume ratio of 1 was added. The solution became turbid. After centrifugation at 3500 rpm, the bottom precipitate was taken and dispersed again in a mixture of methanol and toluene. The centrifugation was repeated once to obtain indium antimonide quantum dots.
[0055] (7) Take an appropriate amount of the above-mentioned indium antimonide quantum dots and perform transmission electron microscopy (TEM) analysis to determine the size distribution and morphology. Figure 1 As shown, the prepared indium antimonide quantum dots are in the form of fragments, and their average lateral size is 9.8 nm. The indium antimonide quantum dots are uniform in size and have good monodispersity.
[0056] Embodiment 2:
[0057] This embodiment is basically similar to embodiment 1, the main difference being that trioctylphosphine is introduced as a ligand after the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution are mixed. The main steps are as follows:
[0058] (1) 3.4 mL of toluene and 0.6 mL of oleylamine were mixed, 1.56 mmol of InCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M indium precursor solution.
[0059] (2) 3.4 mL of ethanol and 0.6 mL of oleylamine were mixed, 1.56 mmol of SbCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M antimony precursor solution.
[0060] (3) 1.5 ml of oleylamine was injected into a three-necked flask, and the temperature was raised to 160° C. and maintained for 5 min under inert atmosphere protection. 1.5 mL of 1 M lithium triethylborohydride n-octyl ether solution was injected, and the temperature was continued to be heated and stirred to stabilize at 160° C. 0.1 mL of indium precursor solution was rapidly injected into the above solution, wherein the molar ratio of lithium triethylborohydride to indium was 40, and after heating for 30 s, the reaction liquid was cooled to room temperature in an ice water bath to obtain an indium nanocrystal precursor solution.
[0061] (4) 1.5 mL of oleylamine was injected into a three-necked flask, and the temperature was raised to 160° C. and maintained for 5 min under an inert atmosphere. 0.4 mL of 2 M lithium diisopropylamide solution was injected, and the temperature was continued to be heated and stirred to stabilize at 160° C. 0.1 mL of antimony precursor solution was quickly injected into the above solution, wherein the ratio of lithium diisopropylamide to antimony was 20. After heating for 1 min, the reaction liquid was cooled to room temperature in an ice water bath to obtain an antimony nanocrystal precursor solution.
[0062] (5) After mixing the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, 0.5 mL of trioctylphosphine was added, and the temperature was raised to 240° C. at 3° C. / min and maintained for 30 min to obtain an indium antimonide quantum dot mixed solution.
[0063] (6) Oleic acid was added to the mixture and stirred for 10 min. A mixture of methanol and toluene in a volume ratio of 1 was added, and the solution became turbid. After centrifugation at 3500 rpm, the bottom precipitate was taken and dispersed again in the mixture of methanol and toluene. The centrifugation was repeated once to obtain indium antimonide quantum dots.
[0064] (7) Take an appropriate amount of the above-mentioned indium antimonide quantum dots and perform transmission electron microscopy (TEM) analysis to determine the size distribution and morphology. Figure 2 As shown, the prepared indium antimonide quantum dots are spherical particles with an average size of 7.6 nm. The indium antimonide quantum dots are uniform in size and have good monodispersity.
[0065] Embodiment 3:
[0066] This embodiment is basically similar to embodiment 1, the main difference being that trioctylphosphine is introduced when synthesizing indium nanocrystals and antimony nanocrystals. The main steps are as follows:
[0067] (1) 3.4 mL of toluene and 0.6 mL of oleylamine were mixed, 1.56 mmol of InCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M indium precursor solution.
[0068] (2) 3.4 mL of ethanol and 0.6 mL of oleylamine were mixed, 1.56 mmol of SbCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M antimony precursor solution.
[0069] (3) 1.2 mL of oleylamine and 0.3 mL of trioctylphosphine were injected into a three-necked flask, heated to 160°C and maintained for 5 min under inert atmosphere, and 1.5 mL of 1 M lithium triethylborohydride n-octyl ether solution was injected, and heating and stirring were continued to stabilize at 160°C. 0.1 mL of indium precursor solution was quickly injected into the above solution, and after heating for 30 seconds, the reaction liquid was cooled to room temperature in an ice water bath to obtain an indium nanocrystal precursor solution.
[0070] (4) 1.2 mL of oleylamine and 0.3 mL of trioctylphosphine were injected into a three-necked flask, and the temperature was raised to 160° C. and maintained for 5 min under an inert atmosphere. 0.4 mL of 2 M lithium diisopropylamide was injected, and the temperature was continued to be heated and stirred to stabilize at 160° C. 0.1 mL of antimony precursor solution was quickly injected into the above solution, and after heating for 1 min, the reaction liquid was cooled to room temperature in an ice water bath to obtain an antimony nanocrystal precursor solution.
[0071] (5) After mixing the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, the temperature was raised to 240° C. at a rate of 3° C. / min and maintained for 30 min to obtain an indium antimonide quantum dot mixed solution.
[0072] (6) Oleic acid was added to the mixture and stirred for 10 min. A mixture of methanol and toluene in a volume ratio of 1 was added, and the solution became turbid. After centrifugation at 3500 rpm, the bottom precipitate was taken and dispersed again in the mixture of methanol and toluene. The centrifugation was repeated once to obtain indium antimonide quantum dots.
[0073] (7) Take an appropriate amount of the above-mentioned indium antimonide quantum dots and perform transmission electron microscopy (TEM) analysis to determine the size distribution and morphology. Figure 3 As shown, the prepared indium antimonide quantum dots are worm-shaped, and their lateral dimensions are between 5 and 20 nm. The indium antimonide quantum dots are uniform in size and have good monodispersity.
[0074] Embodiment 4:
[0075] This embodiment is basically similar to embodiment 1, the main difference being that the heating temperature is changed. The main steps are as follows:
[0076] (1) 3.4 mL of toluene and 0.6 mL of oleylamine were mixed, 1.56 mmol of InCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M indium precursor solution.
[0077] (2) 3.4 mL of ethanol and 0.6 mL of oleylamine were mixed, 1.56 mmol of SbCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M antimony precursor solution.
[0078] (3) 1.5 mL of oleylamine was injected into a three-necked flask, and the temperature was raised to 160° C. and maintained for 5 min under an inert atmosphere. 1.5 mL of 1 M lithium triethylborohydride n-octyl ether solution was injected, and the temperature was continued to be heated and stirred to stabilize at 160° C. 0.1 mL of indium precursor solution was quickly injected into the above solution, and after heating for 30 s, the reaction liquid was cooled to room temperature in an ice water bath to obtain an indium nanocrystal precursor solution.
[0079] (4) 1.5 mL of oleylamine was injected into a three-necked flask, and the temperature was raised to 160°C and maintained for 5 min under an inert atmosphere. 0.4 mL of 2 M lithium diisopropylamide was injected, and the temperature was continued to be heated and stirred to stabilize at 160°C. 0.1 mL of antimony precursor solution was quickly injected into the above solution, and after heating for 1 min, the reaction liquid was cooled to room temperature in an ice water bath to obtain an antimony nanocrystal precursor solution.
[0080] (5) After mixing the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, the temperature was raised to 260° C. at a rate of 3° C. / min and maintained for 30 min to obtain an indium antimonide quantum dot mixed solution.
[0081] (6) Oleic acid was added to the mixture and stirred for 10 min. A mixture of methanol and toluene in a volume ratio of 1 was added, and the solution became turbid. After centrifugation at 3500 rpm, the bottom precipitate was taken and dispersed again in the mixture of methanol and toluene. The centrifugation was repeated once to obtain indium antimonide quantum dots.
[0082] (7) Take an appropriate amount of the above-mentioned indium antimonide quantum dots and perform transmission electron microscopy (TEM) analysis to determine the size distribution and morphology. Figure 4 As shown, the prepared indium antimonide quantum dots are quasi-spherical particles with an average size of 16.9 nm. The indium antimonide quantum dots are uniform in size and have good monodispersity.
[0083] Embodiment 5:
[0084] This embodiment is basically similar to embodiment 1, the main difference being that diisopropylamine lithium ion and triethylborohydride lithium are simultaneously introduced into the preparation of antimony nanocrystals and indium nanocrystals. The main steps are as follows:
[0085] (1) 3.4 mL of toluene and 0.6 mL of oleylamine were mixed, 1.56 mmol of InCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M indium precursor solution.
[0086] (2) 3.4 mL of ethanol and 0.6 mL of oleylamine were mixed, 1.56 mmol of SbCl3 was added, and the mixture was heated and stirred at 90°C until it became clear, thereby obtaining a 0.4 M antimony precursor solution.
[0087] (3) 1.5 mL of oleylamine was injected into a three-necked flask, and the temperature was raised to 160°C and maintained for 5 min under inert atmosphere. 0.2 mL of 2 M lithium diisopropylamide was injected, and the temperature was continued to be heated and stirred to stabilize at 160°C. 0.1 mL of indium precursor solution was quickly injected into the above solution to react for 1 min, and 0.2 mL of 1 M lithium triethylborohydride n-octyl ether solution was injected. After heating and reacting for 30 s, the reaction liquid was cooled to room temperature in an ice water bath to obtain an indium nanocrystal precursor solution.
[0088] (4) 1.5 mL of oleylamine was injected into a three-necked flask, and the temperature was raised to 160°C and maintained for 5 min under inert atmosphere. 0.2 mL of 2 M lithium diisopropylamide was injected, and the temperature was continued to be heated and stirred to stabilize at 160°C. 0.1 mL of antimony precursor solution was quickly injected into the above solution, and after heating for 1 min, 0.2 mL of 1 M lithium triethylborohydride n-octyl ether solution was injected, and after heating for 9 min, the reaction liquid was cooled to room temperature in an ice water bath to obtain an antimony nanocrystal precursor solution.
[0089] (5) After mixing the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, the temperature was raised to 240° C. at a rate of 3° C. / min and maintained for 30 min to obtain an indium antimonide quantum dot mixed solution.
[0090] (6) Oleic acid was added to the mixture and stirred for 10 min. A mixture of methanol and toluene in a volume ratio of 1 was added, and the solution became turbid. After centrifugation at 3500 rpm, the bottom precipitate was taken and dispersed again in the mixture of methanol and toluene. The centrifugation was repeated once to obtain indium antimonide quantum dots.
[0091] (7) Take an appropriate amount of the above-mentioned indium antimonide quantum dots and perform transmission electron microscopy (TEM) analysis to determine the size distribution and morphology. Figure 5 As shown, the prepared indium antimonide quantum dots are uniform spherical particles with an average size of 9.6 nm. The indium antimonide quantum dots are uniform in size and have good monodispersity.
[0092] Embodiment 6:
[0093] The X-ray diffraction patterns and UV-visible near-infrared absorption spectra of the synthesized indium antimonide quantum dots in Example 1 are shown in Figures 1 and 2. Figure 6 and Figure 7 shown.
[0094] The X-ray diffraction pattern of the indium antimonide quantum dots prepared in Example 1 shows that the diffraction peaks appear at 23.8°, 39.3°, and 46.5°, corresponding to the 111, 022, and 113 planes of the sphalerite structure, and have good crystallinity ( Figure 6 The UV-visible-near-infrared absorption spectra of the prepared InSb quantum dots are shown in Figure 7 As shown, it has light absorption in the range of 1000nm-2000nm. The specific steps of preparing a photodetector using the above quantum dots are as follows:
[0095] (1) The Si / SiO2 substrate was ultrasonically cleaned with acetone, ethanol and deionized water, and then treated with ultraviolet ozone;
[0096] (2) 10 μL of a quantum dot tetrachloroethylene solution (quantum dot concentration of 5 mg / mL) was spin coated on a Si / SiO2 substrate at a speed of 1500 rpm for 20 seconds, followed by thermal annealing at 100 °C in a nitrogen glove box, and finally, an Au electrode was deposited.
[0097] (3) Perform a photocurrent test on the above-mentioned photoconductive device. The photoelectric response current is as follows: Figure 8 As shown, the photoconductive device exhibits good photo-electric response under excitation of white light (390-780nm), 1050nm and 1550nm light sources.
[0098] The embodiments described above provide a detailed description of the technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, supplements and equivalent substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing InSb quantum dots, characterized in that: include: Indium nanocrystals and antimony nanocrystals are dispersed in an organic solvent and mixed evenly. In the presence of a ligand, the temperature is raised to 60-300° C. and the reaction is carried out for 0.1-120 minutes to obtain InSb quantum dots.
2. The method for preparing InSb quantum dots according to claim 1, characterized in that: include: After indium nanocrystals and antimony nanocrystals are dispersed in an organic solvent and mixed evenly, a ligand is added, and the temperature is raised to 60-300° C. at a heating rate of 1-30° C. / min, and the reaction is carried out for 0.1-120 minutes to obtain InSb quantum dots.
3. The method for preparing InSb quantum dots according to claim 1, characterized in that: The ligand is at least one of tertiary alkyl phosphine, secondary alkyl phosphine, aromatic phosphine and fatty acid; the organic solvent is at least one of fatty amine and olefin; in the reaction system, the molar ratio of the ligand to the indium nanocrystal or antimony nanocrystal is greater than 0.
1.
4. The method for preparing InSb quantum dots according to claim 1, characterized in that: The preparation method of indium nanocrystals is as follows: in an inert atmosphere at 40-300° C., reacting an indium precursor with a reducing agent and / or an organic base for 0.1-30 minutes to obtain indium nanocrystals; The preparation method of antimony nanocrystals is as follows: in an inert atmosphere at 40-300° C., an antimony precursor reacts with a reducing agent and / or an organic base for 0.1-30 minutes to obtain antimony nanocrystals.
5. The method for preparing InSb quantum dots according to claim 4, characterized in that: The method for preparing indium nanocrystals comprises: (1-1) dissolving an indium precursor in a mixture of toluene and aliphatic amine to form an indium precursor solution; (1-2) Under an inert atmosphere, the solvent is heated to a temperature of K1, an indium precursor solution is added, an organic base is added or not added, and the reaction is continued for T1 time, and then a reducing agent is added. The reaction is continued for T2 time, and then the reaction is cooled to obtain an indium nanocrystal precursor solution. The method for preparing antimony nanocrystals comprises: (2-1) dissolving an antimony precursor in a mixture of toluene and aliphatic amine to form an antimony precursor solution; (2-2) Under an inert atmosphere, the solvent is heated to K2 temperature, an antimony precursor solution is added, an organic base is added or not added, and the reaction is continued for T3 time, and then a reducing agent is added. The reaction is continued for T4 time and then cooled to obtain an antimony nanocrystal precursor solution.
6. The method for preparing InSb quantum dots according to claim 5, characterized in that: After mixing the indium nanocrystal precursor solution and the antimony nanocrystal precursor solution, adding the ligand, heating to 60-300° C. at a heating rate of 1-30° C. / min, reacting for 0.1-120 min, and obtaining InSb quantum dots.
7. The method for preparing InSb quantum dots according to claim 4, characterized in that: The indium precursor is at least one of indium chloride, indium bromide, indium iodide, indium acetate, and indium carboxylate; the antimony precursor is at least one of antimony chloride, antimony bromide, antimony iodide, and tris(dimethylamino)antimony; The reducing agent is at least one of lithium triethylborohydride, sodium borohydride, diisobutylaluminum hydride, and N,N-dimethylethamine aldehyde alkane complex; and the organic base is an organic base with a pKa greater than 15.
8. The method for preparing InSb quantum dots according to claim 5, characterized in that: K1 temperature and K2 temperature are independently 40-300°C; T1 time, T2 time, T3 time, and T4 time are independently 0-10 min.
9. An InSb quantum dot prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the InSb quantum dots according to claim 9 in preparing colloidal quantum dot infrared detectors, solar cells or light-emitting devices.
Citation Information
Patent Citations
GaSb-based InSb quantum dot and preparation method thereof
CN111244761A
Indium antimonide crystal and preparation method thereof
CN115726042A