CN114933898B - Preparation method of transition metal element doped lead sulfide quantum dot - Google Patents
Preparation method of transition metal element doped lead sulfide quantum dot Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 75
- 229940056932 lead sulfide Drugs 0.000 title claims abstract description 28
- 229910052981 lead sulfide Inorganic materials 0.000 title claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 64
- 239000002243 precursor Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011550 stock solution Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 13
- 229940046892 lead acetate Drugs 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 9
- -1 transition metal salt Chemical class 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 4
- 238000006862 quantum yield reaction Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 229910020282 Pb(OH) Inorganic materials 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004054 semiconductor nanocrystal Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/661—Chalcogenides
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- C09K11/892—Chalcogenides
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Abstract
The invention belongs to the field of preparation of semiconductor nano materials, and particularly relates to a preparation method of a transition metal element doped lead sulfide quantum dot. The synthesis method of the invention comprises the following steps: synthesizing a micron/submicron lead source doped with transition metal ions by an aqueous solution precipitation method, then reacting the lead source with an organic reagent to form a lead precursor, rapidly injecting elemental sulfur dissolved in oleylamine into a lead precursor solution at a certain temperature under a nitrogen protective atmosphere, controlling reaction parameters to obtain a lead sulfide colloidal quantum dot stock solution doped with transition metal elements, centrifuging to remove impurities, and purifying to obtain the lead sulfide colloidal quantum dots doped with transition metal elements. The preparation method is simple and controllable, and the prepared quantum dots have adjustable optical performance, good stability and high fluorescence quantum yield, and can be used for preparing high-quality doped quantum dots in batches.
Description
Technical Field
The invention belongs to the field of preparation of semiconductor nano materials, and particularly relates to a preparation method of a transition metal element doped lead sulfide quantum dot.
Background
Quantum dots are zero-dimensional semiconductors, which have very unique optical and electrical properties due to space constraints. The lead sulfide (PbS) quantum dot is an IV-VI semiconductor nanomaterial and has high fluorescence quantum yield in a near infrared band.
At present, according to the preparation principle of quantum dots which grow slowly at low temperature and are rapidly nucleated at high temperature, a thermal injection method is often adopted to synthesize the lead sulfide quantum dots. Many reports on the synthesis of high-quality quantum dots exist, but the problems of complex synthesis process, long reaction period, poor particle uniformity and the like are not solved effectively, so that the development of a green and simple method for preparing the high-quality lead sulfide quantum dots is necessary.
The doped quantum dot is a semiconductor nanocrystal formed by doping a small amount of rare earth ions or transition metal ions into a crystal lattice of a pure quantum dot. The transition metal doped quantum dot has the characteristics of zero self-absorption, wider emission spectrum range, better photochemical stability and the like. The simple lead sulfide quantum dot has poor stability, and the problem of oxidization under the conditions of air and illumination is difficult to avoid. The crystal defect of lead sulfide can be effectively reduced by doping transition metal ions, and the stability of the optical performance of the quantum dot is improved, so that the photoelectric conversion efficiency of the quantum dot is improved. At present, a nucleation doping mode and a growth doping mode are mostly adopted. The nucleation doping mode is to introduce a doping agent in the process of nucleating the semiconductor nano-crystal so as to enable doped ions to grow together with the nano-material; the growth doping mode is a method of doping transition metal ions after the quantum dots are nucleated, so that the ions are adsorbed on the surface of the semiconductor nano material and continue to grow.
Disclosure of Invention
In order to solve the problems in the prior art of doped quantum dot synthesis, the invention provides a preparation method of a convenient and controllable transition metal element doped lead sulfide colloid quantum dot. The obtained quantum dot has uniform size and shape, high fluorescence efficiency and good light stability. The method comprises the following steps:
(1) Respectively weighing sodium chloride, basic lead acetate and a transition metal salt doping agent to prepare an aqueous solution with a certain concentration, then firstly mixing the basic lead acetate and the transition metal salt doping agent solution together, finally slowly adding the sodium chloride solution, reacting for 10-60 min at a certain temperature to obtain a precipitate, washing with distilled water and drying to obtain a doped lead source;
(2) Under the protection of nitrogen, heating and reacting the lead source synthesized in the step (1) with an organic reagent for a period of time at 90-160 ℃, and vacuumizing to obtain a lead precursor;
(3) Mixing elemental sulfur and oleylamine at normal temperature to prepare sulfur precursor solution with certain concentration; then, a certain volume of sulfur precursor solution is rapidly injected into the lead precursor solution with the temperature set and recovered under the protection of nitrogen in the step (2); finally, cooling to 10-25 ℃ after reacting for 0.5-20 min at constant temperature, and stopping reacting to obtain the lead sulfide colloid quantum dot stock solution doped with the transition metal element;
(4) Centrifuging the quantum dot solution obtained in the step (3) to remove impurities, diluting with a quantum dot solvent, purifying the quantum dot solution with a strong polar organic solvent, centrifuging again, and redissolving the solid quantum dots obtained after separation in a specific solvent to obtain a transition metal element doped lead sulfide colloidal quantum dot solution.
More preferably, the concentration of the sodium chloride and the basic lead acetate in the step (1) is 0.2M-2M; the transition metal salt is Mn, hg, ni, co, cu, fe, zn salt which can be dissolved in distilled water; the molar ratio of the transition metal salt to basic lead acetate is 1: 40-1: 10; the reaction temperature is 25-90 ℃; the lead source has any shape with micron or submicron size;
more preferably, the organic reagent in the step (2) is at least two of octylamine, oleylamine, oleic acid and octadecene;
more preferably, the concentration of the sulfur precursor solution in the step (3) is 0.1M-0.5M; the temperature of the lead precursor in the step (3) is 60-160 ℃ during sulfur injection;
more preferably, the quantum dot solvent in the step (4) is one of toluene, chloroform and hexane; the polar organic solvent is at least one of methanol, ethanol, butanol and acetone, preferably ethanol and acetone; the specific solvent is at least one of toluene, chloroform, hexane, decane and decene; the first exciton absorption peak range of the PbS colloid quantum dot is 1000 nm-2000 nm.
Before the process of synthesizing the doped quantum dots, transition metal ions are directly doped into a lead source by an aqueous solution precipitation method, so that the process operation is simplified, the reaction variable is reduced, the size of the quantum dots is favorably regulated and controlled, and the finally obtained high-quality quantum dots are improved. The preparation method is simple and controllable, and the prepared quantum dots have adjustable optical performance, good stability and high fluorescence quantum yield, and can be used for preparing high-quality doped quantum dots in batches.
Compared with the prior art, the invention has the beneficial effects that:
(1) The chemical reagent used has stable property and can be stored at normal temperature and normal pressure;
(2) The lead source is not needed to be excessive, so that the waste of the lead source is avoided, and the manufacturing process is concise and environment-friendly;
(3) The size, quality and light absorption range of the quantum dot can be regulated and controlled by changing the doping proportion of the transition metal element, the injection temperature of the precursor and the reaction time.
Detailed Description
Further details of the preparation process according to the invention are given below in connection with specific examples. It is to be understood that the following examples are only for the purpose of illustrating the present invention and that the implementation of variations or modifications of the invention using the technical idea of the present invention falls within the scope of the appended claims.
Example 1
A: 1.2g of sodium chloride and 6g of lead basic acetate (Pb (CH) 3 COO) 2 ·Pb(OH) 2 ) 0.06g of manganese chloride was dissolved in 15ml of distilled water to prepare 1.37M, 0.7M and 0.032M solutions, respectively; firstly, mixing basic lead acetate and manganese chloride solution, then slowly dropwise adding sodium chloride solution, reacting at 80 ℃ for 15min to obtain precipitate, washing with distilled water and drying to obtain a lead source doped with manganese; mixing and stirring 0.3g of synthesized lead source with 15ml of octylamine/oleic acid/octadecylene/oleylamine, introducing protective gas nitrogen, heating to 120 ℃ for reaction for 40min, and vacuumizing for 40min to obtain manganese-doped lead precursor solution;
b: mixing 0.032g of elemental sulfur with 3.5ml of oleylamine at normal temperature, and rapidly dissolving the elemental sulfur under the action of ultrasound to obtain 0.286M sulfur precursor solution; then rapidly injecting the sulfur precursor solution into the lead precursor solution cooled to 70 ℃ in the step A under the nitrogen atmosphere; finally, cooling to 25 ℃ after reacting for 30 seconds at constant temperature, and stopping reacting to obtain manganese-doped lead sulfide colloid quantum dot stock solution;
c: centrifuging the colloidal quantum dot stock solution prepared in the step B to remove unreacted impurities, and dissolving the obtained quantum dots in n-hexane; then ethanol was added to purify the quantum dot solution, and the supernatant was removed to obtain a precipitate, which was redissolved in n-hexane to obtain a manganese-doped lead sulfide colloidal quantum dot solution having a first exciton absorption peak position of 1235nm and a fluorescence efficiency of 65% (table 1).
Example 2
A: 1.2g of sodium chloride and 6g of lead basic acetate (Pb (CH) 3 COO) 2 ·Pb(OH) 2 ) 0.12g of mercuric chloride is dissolved in 15ml of distilled water to prepare solutions of 1.37M, 0.7M and 0.029M respectively; firstly, mixing basic lead acetate and mercury chloride solution, then slowly dropwise adding sodium chloride solution, reacting at 80 ℃ for 15min to obtain precipitate, washing with distilled water and drying to obtain a mercury-doped lead source; mixing and stirring 0.3g of synthesized lead source with 15ml of octylamine/oleic acid/octadecene/oleylamine, introducing protective gas nitrogen, heating to 120 ℃ for reaction for 40min, and vacuumizing for 40min to obtain mercury-doped lead precursor solution;
b: mixing 0.032g of elemental sulfur with 3.5ml of oleylamine at normal temperature, and rapidly dissolving the elemental sulfur under the action of ultrasound to obtain 0.286M sulfur precursor solution; then rapidly injecting the sulfur precursor solution into the lead precursor solution cooled to 70 ℃ in the step A under the nitrogen atmosphere; finally, cooling to 25 ℃ after reacting for 30 seconds at constant temperature, and stopping reacting to obtain a mercury-doped lead sulfide colloid quantum dot stock solution;
c: centrifuging the colloidal quantum dot stock solution prepared in the step B to remove unreacted impurities, and dissolving the obtained quantum dots in n-hexane; then adding ethanol to purify the quantum dot solution, removing the supernatant to obtain precipitate, and redissolving the precipitate in n-hexane to obtain the mercury-doped lead sulfide colloid quantum dot solution with the first exciton absorption peak position of 1365nm and the fluorescence efficiency of 57 percent (table 1).
Example 3
A: 1.2g of sodium chloride and 6g of lead basic acetate (Pb (CH) 3 COO) 2 ·Pb(OH) 2 ) 0.08g of zinc acetate was dissolved in 15ml of distilled water to prepare solutions of 1.37M, 0.7M and 0.029M, respectively; firstly, mixing basic lead acetate and zinc acetate solution, then slowly dripping sodium chloride solution, reacting for 15min at 80 ℃ to obtain precipitate, washing with distilled water and drying to obtain a zinc-doped lead source; mixing and stirring 0.3g of synthesized lead source with 15ml of octylamine/oleic acid/octadecylene/oleylamine, introducing protective gas nitrogen, heating to 120 ℃ for reaction for 40min, and vacuumizing for 40min to obtain zinc-doped lead precursor solution;
b: mixing 0.032g of elemental sulfur with 3.5ml of oleylamine at normal temperature, and rapidly dissolving the elemental sulfur under the action of ultrasound to obtain 0.286M sulfur precursor solution; then rapidly injecting the sulfur precursor solution into the lead precursor solution cooled to 70 ℃ in the step A under the nitrogen atmosphere; finally, cooling to 25 ℃ after reacting for 30 seconds at constant temperature, and stopping reacting to obtain zinc-doped lead sulfide colloid quantum dot stock solution;
c: centrifuging the colloidal quantum dot stock solution prepared in the step B to remove unreacted impurities, and dissolving the obtained quantum dots in n-hexane; then, ethanol was added to purify the quantum dot solution, and the supernatant was removed to obtain a precipitate, which was redissolved in n-hexane to obtain a zinc-doped lead sulfide colloidal quantum dot solution having a first exciton absorption peak position of 1561nm and a fluorescence efficiency of 45% (table 1).
Example 4
A: 1.2g of sodium chloride and 6g of lead basic acetate (Pb (CH) 3 COO) 2 ·Pb(OH) 2 ) 0.08g of cobalt nitrate was dissolved in 15ml of distilled water to prepare solutions of 1.37M, 0.7M and 0.029M, respectively; firstly, mixing basic lead acetate and cobalt nitrate solution, then slowly dropwise adding sodium chloride solution, reacting at 80 ℃ for 15min to obtain precipitate, washing with distilled water and drying to obtain a cobalt-doped lead source; mixing and stirring 0.3g of synthesized lead source with 15ml of octylamine/oleic acid/octadecylene/oleylamine, introducing protective gas nitrogen, heating to 120 ℃ for reaction for 40min, and vacuumizing for 40min to obtain a cobalt-doped lead precursor solution;
b: mixing 0.032g of elemental sulfur with 3.5ml of oleylamine at normal temperature, and rapidly dissolving the elemental sulfur under the action of ultrasound to obtain 0.286M sulfur precursor solution; then rapidly injecting the sulfur precursor solution into the lead precursor solution cooled to 70 ℃ in the step A under the nitrogen atmosphere; finally, cooling to 25 ℃ after reacting for 30 seconds at constant temperature, and stopping reacting to obtain cobalt-doped lead sulfide colloid quantum dot stock solution;
c: centrifuging the colloidal quantum dot stock solution prepared in the step B to remove unreacted impurities, and dissolving the obtained quantum dots in n-hexane; then ethanol was added to purify the quantum dot solution, and the supernatant was removed to obtain a precipitate, which was redissolved in n-hexane to obtain a cobalt-doped lead sulfide colloidal quantum dot solution having a first exciton absorption peak of 1450nm and a fluorescence efficiency of 62% (table 1).
Example 5
A: 1.2g of sodium chloride and 6g of lead basic acetate (Pb (CH) 3 COO) 2 ·Pb(OH) 2 ) 0.06g of copper chloride was dissolved in 15ml of distilled water to prepare 1.37M, 0.7M and 0.03M solutions, respectively; firstly, mixing basic lead acetate and copper chloride solution, then slowly dropwise adding sodium chloride solution, reacting for 15min at 80 ℃ to obtain precipitate, washing with distilled water and drying to obtain a copper-doped lead source; mixing and stirring 0.3g of synthesized lead source and 15ml of octylamine/oleic acid/octadecene/oleylamine, introducing protective gas nitrogen, heating to 120 ℃ for reaction for 40min, and vacuumizing for 40min to obtain copper-doped lead precursor solution;
b: mixing 0.032g of elemental sulfur with 3.5ml of oleylamine at normal temperature, and rapidly dissolving the elemental sulfur under the action of ultrasound to obtain 0.286M sulfur precursor solution; then rapidly injecting the sulfur precursor solution into the lead precursor solution cooled to 70 ℃ in the step A under the nitrogen atmosphere; finally, cooling to 25 ℃ after reacting for 30 seconds at constant temperature, and stopping reacting to obtain copper-doped lead sulfide colloid quantum dot stock solution;
c: centrifuging the colloidal quantum dot stock solution prepared in the step B to remove unreacted impurities, and dissolving the obtained quantum dots in n-hexane; then, ethanol was added to purify the quantum dot solution, and the supernatant was removed to obtain a precipitate, which was redissolved in n-hexane to obtain a copper-doped lead sulfide colloidal quantum dot solution having a first exciton absorption peak of 1815nm and a fluorescence efficiency of 30% (table 1).
TABLE 1 first exciton absorption peak position of PbS colloid Quantum dots synthesized by examples
The foregoing description of the preferred embodiments of the present invention has been presented only in terms of those specific and detailed descriptions, and is not, therefore, to be construed as limiting the scope of the invention. It should be noted that modifications, improvements and substitutions can be made by those skilled in the art without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
1. The preparation method of the transition metal element doped lead sulfide quantum dot is characterized by comprising the following steps of:
(1) Respectively weighing sodium chloride, basic lead acetate and a transition metal salt doping agent to prepare an aqueous solution with a certain concentration, then mixing the basic lead acetate and the transition metal salt doping agent solution together, finally slowly adding the sodium chloride solution, reacting for 10-60 min at a certain temperature to obtain a precipitate, washing with distilled water, and drying to obtain a doped lead source; the transition metal salt is Mn, hg, co, cu, zn salt;
(2) Under the protection of nitrogen, heating and reacting the lead source synthesized in the step (1) with an organic reagent for a period of time at 90-160 ℃, and vacuumizing to obtain a lead precursor;
(3) Mixing elemental sulfur and oleylamine at normal temperature to prepare sulfur precursor solution with certain concentration; then, a certain volume of sulfur precursor solution is rapidly injected into the lead precursor solution with the temperature set and recovered under the protection of nitrogen in the step (2); finally, cooling to 10-25 ℃ after reacting for 0.5-20 min at constant temperature, and stopping reacting to obtain a lead sulfide colloid quantum dot stock solution doped with transition metal elements;
(4) Centrifuging the quantum dot solution obtained in the step (3) to remove impurities, diluting with a quantum dot solvent, purifying the quantum dot solution with a strong polar organic solvent, centrifuging again, and redissolving the solid quantum dots obtained after separation in a specific solvent to obtain a transition metal element doped lead sulfide colloidal quantum dot solution.
2. The method for preparing the transition metal element doped lead sulfide quantum dot according to claim 1, which is characterized by comprising the following steps: the concentration of the sodium chloride and the basic lead acetate in the step (1) is 0.2-2M; the molar ratio of the transition metal salt to basic lead acetate is 1: 40-1: 10; the reaction temperature is 25-90 ℃; the lead source has any morphology of micron or submicron size.
3. The method for preparing the transition metal element doped lead sulfide quantum dot according to claim 1, which is characterized by comprising the following steps: the organic reagent in the step (2) is at least two of octylamine, oleylamine, oleic acid and octadecene.
4. The method for preparing the transition metal element doped lead sulfide quantum dot according to claim 1, which is characterized by comprising the following steps: the concentration of the sulfur precursor solution in the step (3) is 0.1M-0.5M; the temperature of the lead precursor in the step (3) is 60-160 ℃ during sulfur injection.
5. The method for preparing the transition metal element doped lead sulfide quantum dot according to claim 1, which is characterized by comprising the following steps: the quantum dot solvent in the step (4) is one of toluene, chloroform and hexane; the polar organic solvent is at least one of methanol, ethanol, butanol and acetone; the specific solvent is at least one of toluene, chloroform, hexane, decane and decene; the first exciton absorption peak range of the PbS colloid quantum dot is 1000 nm-2000 nm.
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| CN110697766A (en) * | 2019-09-30 | 2020-01-17 | 武汉理工大学 | Preparation method of zinc-doped lead sulfide quantum dots |
| CN111635759A (en) * | 2020-06-16 | 2020-09-08 | 南昌大学 | Preparation method of lead sulfide colloidal quantum dots |
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| CN110697766A (en) * | 2019-09-30 | 2020-01-17 | 武汉理工大学 | Preparation method of zinc-doped lead sulfide quantum dots |
| CN111635759A (en) * | 2020-06-16 | 2020-09-08 | 南昌大学 | Preparation method of lead sulfide colloidal quantum dots |
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| Band gap tuning and fluorescence properties of lead sulfide Pb0.9A0.1S(A: Fe, Co, and Ni) nanoparticles by transition metal doping;Azra Parveen等;《Optical Materials》;20171207;第76卷;第21-27页 * |
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