CN114958341A - InP quantum dot and preparation method thereof - Google Patents
InP quantum dot and preparation method thereof Download PDFInfo
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- CN114958341A CN114958341A CN202210840748.7A CN202210840748A CN114958341A CN 114958341 A CN114958341 A CN 114958341A CN 202210840748 A CN202210840748 A CN 202210840748A CN 114958341 A CN114958341 A CN 114958341A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 157
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 71
- 239000011574 phosphorus Substances 0.000 claims abstract description 71
- 239000000956 alloy Substances 0.000 claims abstract description 57
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 57
- 239000013078 crystal Substances 0.000 claims abstract description 51
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 229910052738 indium Inorganic materials 0.000 claims description 63
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 63
- 239000003446 ligand Substances 0.000 claims description 60
- 239000011701 zinc Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 35
- 239000000376 reactant Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 28
- 239000012682 cationic precursor Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
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- OUMZKMRZMVDEOF-UHFFFAOYSA-N tris(trimethylsilyl)phosphane Chemical compound C[Si](C)(C)P([Si](C)(C)C)[Si](C)(C)C OUMZKMRZMVDEOF-UHFFFAOYSA-N 0.000 claims description 4
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- SKWCWFYBFZIXHE-UHFFFAOYSA-K indium acetylacetonate Chemical compound CC(=O)C=C(C)O[In](OC(C)=CC(C)=O)OC(C)=CC(C)=O SKWCWFYBFZIXHE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 3
- FDIOSTIIZGWENY-UHFFFAOYSA-N n-[bis(diethylamino)phosphanyl]-n-ethylethanamine Chemical compound CCN(CC)P(N(CC)CC)N(CC)CC FDIOSTIIZGWENY-UHFFFAOYSA-N 0.000 claims description 3
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- DDQMTQUVWRTBIV-UHFFFAOYSA-N tris(triethylsilyl)phosphane Chemical compound CC[Si](CC)(CC)P([Si](CC)(CC)CC)[Si](CC)(CC)CC DDQMTQUVWRTBIV-UHFFFAOYSA-N 0.000 claims description 3
- LRJNVYLVJPVDOB-UHFFFAOYSA-N tris(triphenylsilyl)phosphane Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)P([Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LRJNVYLVJPVDOB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
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- 150000002500 ions Chemical class 0.000 description 4
- 210000004940 nucleus Anatomy 0.000 description 4
- PORPENFLTBBHSG-MGBGTMOVSA-N 1,2-dihexadecanoyl-sn-glycerol-3-phosphate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(O)=O)OC(=O)CCCCCCCCCCCCCCC PORPENFLTBBHSG-MGBGTMOVSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 3
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- 229910001449 indium ion Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 229910004613 CdTe Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- MJNSMKHQBIVKHV-UHFFFAOYSA-N selenium;trioctylphosphane Chemical compound [Se].CCCCCCCCP(CCCCCCCC)CCCCCCCC MJNSMKHQBIVKHV-UHFFFAOYSA-N 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
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- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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Abstract
InP quantum dots and a preparation method thereof belong to the field of photoelectric materials. The preparation method of the InP quantum dot comprises the following steps: and mixing the InP seed crystal and the Zn-In precursor with lower Zn molar concentration, adding the phosphorus source for curing again after curing, then adding the Zn-In precursor with higher Zn molar concentration again, adding the phosphorus source for curing again after curing, and repeating the steps to obtain the InP-based alloy quantum dot with gradually reduced lattice parameters. And finally, mixing and reacting the InP-based alloy quantum dots with the Zn precursor, the Se precursor and the S precursor to coat ZnSe/ZnS shells on the InP-based alloy quantum dots to form the InP quantum dots. The core-shell structure of the InP quantum dot has higher lattice adaptation degree so as to improve the quantum efficiency of the InP quantum dot.
Description
Technical Field
The application relates to the field of photoelectric materials, in particular to InP quantum dots and a preparation method thereof.
Background
The quantum dots are also called fluorescent semiconductor nanocrystals, have obvious quantum size effect, show unique electronic and optical properties, such as wide excitation spectrum, narrow emission spectrum, adjustable luminescence wavelength along with size components, good light stability and the like, and are always the focus of attention of people due to potential application values in the fields of illumination, display, solar energy, biological marking and the like.
At present, the most applied are binary quantum dots, which are mostly composed of II-VI and IV-VI semiconductor elements, such as CdSe, CdTe, PbS and the like, and contain heavy metal elements such as Cd, Pb and the like, and the potential toxicity greatly limits the practical application.
The InP quantum dots do not contain heavy metal elements, the toxicity is far less than that of a II-VI family Cd class quantum dot material, the glass radius of the InP quantum dots is about 10nm (the block bandwidth is 1.35eV), the effective control of an emission peak from blue light (460nm) to near infrared light (750 nm) can be realized by adjusting the size of the quantum dots, and the InP quantum dots are an ideal nanometer material for replacing the Cd class quantum dots. And the InP quantum dots are direct band gap semiconductors and have high dielectric constants. Due to the unique properties of InP quantum dots, the InP quantum dots are widely applied to the fields of optical communication, detection, light-emitting diodes, biological imaging and the like.
In InP synthesis, the prior art has the defects of low quantum efficiency, weak stability and the like. The covalent property of the InP quantum dot is strong, the surface defects of the core quantum dot are more, the quantum dot efficiency is low, and an effective passivation shell layer is coated on the surface of the InP quantum dot in order to improve the quantum efficiency and stability of the InP quantum dot. At present, for InP quantum dots, ZnS or ZnSe/ZnS passivated shells are mainly used as the passivated shells. However, the core-shell structure of the InP quantum dots coated with a passivated shell layer prepared in the prior art is difficult to adapt, and the quantum efficiency is finally affected, which limits the practical application of the InP quantum dots. Therefore, the method for synthesizing the InP quantum dots with high quantum efficiency and high stability is developed, and has great significance for the use and development of the InP quantum dots.
Disclosure of Invention
Based on the above disadvantages, the present application provides an InP quantum dot and a method for preparing the same, so as to partially or completely improve, and even solve, the problems of low quantum efficiency and poor stability in the related art.
The application is realized as follows:
in a first aspect, examples of the present application provide a method for preparing InP quantum dots, comprising:
(1) mixing InP crystal seeds and a first Zn-In precursor, then performing first curing, adding a first phosphorus source, and performing second curing to obtain a first reactant; wherein the molar ratio of the first phosphorus source to In the first Zn-In precursor is 1: 0.8-4;
(2) mixing the first reactant with a second Zn-In precursor, then carrying out third curing, adding a second phosphorus source, and carrying out fourth curing to obtain a second reactant; wherein the second reactant contains InP-based alloy quantum dots, and the molar ratio of the second phosphorus source to In the second Zn-In precursor is 1: 0.8-4;
wherein the molar concentration of Zn In the first Zn-In precursor is less than the molar concentration of Zn In the second Zn-In precursor;
(3) and mixing and reacting reactants containing the InP-based alloy quantum dots with a Zn precursor, a Se precursor and an S precursor to coat a ZnSe/ZnS shell layer on the InP-based alloy quantum dots to form the InP quantum dots.
In the implementation process, the covalent property of the InP crystal seed is strong, the surface defects of the crystal seed are more, the efficiency of the quantum dot is low, and in order to improve the quantum efficiency and stability of the InP quantum dot, the surface of the InP crystal seed needs to be coated with an effective passivation shell layer ZnSe/ZnS. The lattice parameters of the InP crystal seeds are 5.93A, the lattice parameters of ZnSe and ZnS are 5.66A and 5.42A respectively, and the problem that the lattice mismatch influences the efficiency of the quantum dots exists when the surface of the InP crystal seeds is directly coated with the ZnSe/ZnS of the passivation shell. Therefore, a first Zn-In precursor and a first phosphorus source are injected into the InP seed crystal, a second Zn-In precursor and a second phosphorus source are injected after reaction, and the molar concentration of Zn In the first Zn-In precursor is less than that In the second Zn-In precursor, so that a transition layer with a reduced lattice parameter is grown on the surface of the InP seed crystal. And with the increasing of the molar concentration of Zn, the lattice parameter of the transition layer is decreased gradually, so that the lattice parameter of the InP seed crystal is slowly decreased to obtain the InP-based alloy quantum dot. And then, the surface of the InP-based alloy quantum dot with slowly reduced lattice parameters reacts to generate a passivation shell ZnSe/ZnS, so that the lattice mismatch between an InP crystal nucleus and the passivation shell ZnSe/ZnS is avoided, and the efficiency and the stability of the InP quantum dot are improved.
And adding a first phosphorus source and a first Zn-In precursor according to the molar ratio of 1: 0.8-4 In the step (1), injecting the first Zn-In precursor, curing, and then injecting the first phosphorus source, so that cations In the first Zn-In precursor can be bonded with unsaturated bonds and dangling bonds on the surface of an InP crystal nucleus In the curing process to form the stable indium-rich quantum dots. And then injecting a first phosphorus source with a proper proportion after curing so that the indium-rich quantum dots can be fully grown. If the first phosphorus source injected into the indium-rich quantum dot system is too little, the quantum dots cannot grow fully, and the indium content of the finally obtained quantum dots is increased, so that the optical performance of the quantum dots is poor; if the first phosphorus source injected into the indium-rich quantum dot system is excessive, the growth of the quantum dots can be in a disordered state, and the uniformity of the quantum dots is reduced. Similarly, In the step (2), a first Zn-In precursor is injected into the reactant formed In the step (1), and after curing, a first phosphorus source is injected for curing again to promote uniform growth of the alloy quantum dots.
With reference to the first aspect, in a first possible implementation manner of the first aspect of the present application, after step (2) and before step (3), the method further includes:
mixing the second reactant with a third Zn-In precursor, performing fifth curing, adding a third phosphorus source, and performing sixth curing to obtain a third reactant; the third reactant contains InP-based alloy quantum dots, and the molar ratio of the third phosphorus source to In the third Zn-In precursor is 1: 0.8-4;
the molar concentration of Zn In the third Zn-In precursor is greater than the molar concentration of Zn In the second Zn-In precursor.
In the implementation process, a third Zn-In precursor with higher Zn molar concentration is added into the reactant obtained In the step (2), and curing is performed, so that indium-rich quantum dots are continuously formed on the InP-based alloy quantum dots obtained In the step (2) to be convenient for reacting with a subsequently added third phosphorus source, InP-based alloy quantum dots with lower lattice parameters are formed, further, the lattice matching degree of ZnSe/ZnS of a passivation shell layer and the InP-based alloy quantum dots is further increased, and the efficiency and stability of the InP quantum dots are further improved.
With reference to the first aspect, In a second possible implementation manner of the first aspect of the present application, In step (1), after raising the temperature of the InP seed crystal to a first predetermined temperature and maintaining the temperature for a first predetermined time, a first Zn-In precursor is added; the first preset temperature is 210-260 ℃, and the first preset time is 10-60 min;
the temperature of the first curing, the second curing, the third curing, the fourth curing, the fifth curing and the sixth curing is any temperature within the range of 210-280 ℃.
The InP seed may have some unreacted indium source and even some unreacted anion source in the system, which may adversely affect the subsequent growth of the quantum dots. Therefore, in the implementation process, the InP seed crystal is kept at a certain temperature for a certain time, so that the InP seed crystal system can reach a stable state, and the subsequent growth of InP-based alloy quantum dots is facilitated. And the precursor and the phosphorus source in the system can be promoted to fully react by curing at the temperature of 210-280 ℃, so that the formation of the indium-rich quantum dots and the growth of the InP-based alloy quantum dots are promoted.
With reference to the first aspect, in a third possible implementation manner of the first aspect of the present application, a method for preparing an InP seed crystal includes:
preparation of the cationic precursor:
under an inert atmosphere, mixing the raw materials according to a molar ratio of 1: heating the first indium source and the first ligand which are configured by 0.5-8 to a second preset temperature and keeping the temperature for a second preset time; the second preset temperature is 120-260 ℃, and the second preset time is 30-180 min;
preferably, the first indium source: the molar ratio of the first ligand is 1: 2;
preparing seed crystals:
under an inert atmosphere, keeping the temperature of a mixture of a fourth phosphorus source, a second ligand and a cation precursor at a third preset temperature for a third preset time, and then heating to a fourth preset temperature to obtain InP crystal seeds;
wherein the molar ratio of the fourth phosphorus source to In the cationic precursor is 1: 1-5, wherein the molar ratio of In the cation precursor to the second ligand is 1:0.8 to 8;
preferably, the fourth phosphorus source: the molar ratio of In the cationic precursor is 1: 2;
preferably, the ratio of In: the molar ratio of the second ligand is 1: 2;
the third preset temperature is 30-250 ℃, the third preset time is 5min, and the fourth preset temperature is 230 ℃.
In the implementation process, in order to improve the efficiency and stability of the InP quantum dots, this example also provides a preparation method of an InP seed crystal, so as to prepare an InP seed crystal with better uniformity. The first indium source and the first ligand which are configured according to the molar ratio are reacted at a preset temperature to generate a cation precursor, and the inert atmosphere can prevent the reactant and the generated cation precursor from being oxidized. And (3) keeping the obtained cation precursor, a fourth phosphorus source and a second ligand at a third preset temperature for a third preset time to obtain a cluster containing both cations and anions, and then raising the temperature to a fourth preset temperature to enable the cluster to perform nucleation growth so as to obtain the InP seed crystal.
And, since the molar ratio of the first indium source and the first ligand in the cationic precursor directly affects the size dispersibility of the InP quantum dots, the performance of the quantum dots is ultimately affected. Thus, the first indium source and first ligand molar ratio is limited in this example to 1: 0.5-8, so that the cationic precursor obtained by using a proper feeding ratio reacts with the fourth phosphorus source to grow the seed crystal with more uniform size and monodispersity.
The amount of the second ligand directly affects the reaction rate and product quality of the indium ions in the cationic precursor and the fourth phosphorus source. Limiting the molar ratio of In the cationic precursor to the second ligand to 1: 0.8-8, which can avoid the disadvantage of reaction control caused by too high reaction speed due to too small dosage of the second ligand; too much secondary ligand is used, which may result in poor or even no quantum dots.
With reference to the first aspect, In a fourth possible embodiment of the first aspect of the present application, a method for preparing a first Zn-In precursor includes:
heating a mixture of a second indium source, a zinc source, a third ligand and a non-coordinating solvent to a second preset temperature in an inert atmosphere, and keeping the temperature for a second preset time, wherein the molar ratio of the second indium source to the third ligand is 1: 0.5-8, and the molar ratio of the second indium source to the zinc source is 1: 0.2-10;
preferably, the second indium source: the molar ratio of the third ligand is 1: 3;
according to the preparation method of the first Zn-In precursor, the molar concentration of a zinc source is adjusted within the range that the molar ratio of a second indium source to the zinc source is 1: 0.2-10 so as to respectively obtain a second Zn-In precursor and a third Zn-In precursor;
preferably, according to the preparation method of the first Zn-In precursor, the second indium source is adjusted: the molar ratio of the zinc source is 1:1, 1:5 and 1:10 to obtain a first Zn-In precursor, a second Zn-In precursor and a third Zn-In precursor.
In the implementation process, under an inert atmosphere, heating a mixture of a second indium source, a zinc source, a third ligand and a non-coordinating solvent to a second preset temperature, keeping the temperature for a second preset time, and limiting the molar ratio of the second indium source to the third ligand to be 1: 0.5-8, so as to obtain a Zn-In precursor for bonding with unsaturated bonds and dangling bonds on the surface of InP seed crystals or InP-based alloy quantum dots to form indium-rich quantum dots.
Adjusting a second indium source: the mol ratio of the zinc source is 1:1, 1:5 and 1:10, so that a first Zn-In precursor, a second Zn-In precursor and a third Zn-In precursor which are increased progressively according to the Zn ion mol concentration gradient are obtained, the phenomenon that the difference of the mol concentration of Zn ions In two adjacent groups of Zn-In precursors is large, the influence of overlarge change amplitude of lattice parameters of InP-based alloy quantum dots obtained by the reaction of the three Zn-In precursors and corresponding phosphorus sources is caused, or the lattice parameters cannot be effectively reduced is avoided, and the stability of the InP-based alloy quantum dots is reduced.
With reference to the first aspect, in a fifth possible implementation manner of the first aspect of the present application, the preparing of the cationic precursor further includes an acid discharge operation:
removing acid gas generated by the reaction while keeping the temperature at the second preset temperature for the second preset time; after the temperature is kept for the second preset time, the temperature is reduced to a fifth preset temperature, the atmosphere state is adjusted to be vacuum, and the temperature is kept for a fifth preset time; the fifth preset temperature is 100-180 ℃, and the fifth preset time is 30-180 min;
and/or the preparation method of the first Zn-In precursor further comprises an acid discharge operation:
removing acid gas generated by the reaction while keeping the temperature at the second preset temperature for the second preset time; after the temperature is kept for the second preset time, the temperature is reduced to a sixth preset temperature, the atmosphere state is adjusted to be vacuum, and the temperature is kept for the sixth preset time; the sixth preset temperature is 100-150 ℃, and the sixth preset time is 30-180 min.
In the implementation process, the acid discharge operation is performed in the preparation process of the cation precursor, and since the first indium source and the first ligand react to generate acid gas in the preparation process of the precursor, if the generated acid gas is not completely removed, the size of the quantum dot is very poor, and even the quantum dot cannot be obtained. In the conventional process for removing acid gas by directly utilizing a vacuum-pumping system, generally, the reaction temperature of the precursor is relatively low (if the temperature is too high, the precursor is also directly pumped out) during vacuum-pumping, and the precursor at this time sometimes has the problem of insufficient reaction, and more acid gas remains. Therefore, in the implementation process, the acid gas is removed by adopting double guarantee, namely the acid gas generated in the reaction process is removed while the temperature is kept at the second preset temperature for the second preset time, so that the condition that the reaction temperature is too low and the reaction is insufficient is avoided. And then after the first indium source and the first ligand react to form a cation precursor, cooling the system to a fifth preset temperature, adjusting the atmosphere state to be vacuum, and further removing residual acid gas by vacuumizing.
Similarly, the acid removal operation is performed during the preparation of the first Zn-In precursor, so that the acid gas can be removed while the formation of the Zn-In precursor is promoted.
With reference to the first aspect, in a sixth possible embodiment of the first aspect of the present application, the preparing of the ZnSe/ZnS shell layer further comprises:
heating a mixed system formed by the Zn precursor and the InP-based alloy quantum dots to 180-340 ℃, and then adding the Se precursor and the S precursor.
In the implementation process, a Zn precursor is mixed with the InP-based alloy quantum dots, then the mixed system is heated to 180-340 ℃, Zn ions are enriched on the surfaces of the InP-based alloy quantum dots conveniently, and finally a Se precursor and an S precursor which react with the Zn ions are added, so that ZnSe/ZnS obtained through reaction is coated on the surfaces of the InP-based alloy quantum dots to form a passivation shell layer.
With reference to the first aspect, In a seventh possible implementation manner of the first aspect of the present application, the first indium source and the second indium source are In 3+ A salt species; optionally, the first indium source and the second indium source are each selected from one or more of indium acetate, indium nitrate, indium acetylacetonate, indium chloride and indium sulfate;
the first ligand and the third ligand are both saturated or unsaturated fatty acid with carbon atoms more than or equal to 6; optionally, the first ligand and the third ligand are each selected from one or more of palmitic acid, oleic acid, myristic acid, palmitic acid, lauric acid, and stearic acid;
the first phosphorus source, the second phosphorus source, the third phosphorus source and the fourth phosphorus source are all selected from one or more of tris (trimethylsilyl) phosphorus, tris (triethylsilyl) phosphorus, tris (triphenylsilyl) phosphorus, tris (dimethylamino) phosphorus and tris (diethylamino) phosphorus;
the second ligand is selected from one or more of oleylamine, trioctylamine, trioctylphosphine, tributylphosphine, triphenylphosphine, dioctylamine, octylamine, dodecylamine and hexadecylamine;
the zinc source is selected from Zn 2+ A salt species; optionally, the zinc source is at least one of zinc acetate, zinc chloride, and zinc stearate;
the non-coordinating solvent comprises octadecene.
With reference to the first aspect, in an eighth possible implementation manner of the first aspect of the present application, the first preset temperature is 220 to 240 ℃, and the first preset time is 20 to 40 min;
and/or the second preset temperature is 200-240 ℃, and the second preset time is 60-90 min;
and/or the third preset temperature is 130-170 ℃, and the third preset time is 5 min;
and/or the fifth preset temperature is 150-180 ℃, and the fifth preset time is 60-90 min;
and/or the sixth preset temperature is 120-130 ℃, and the sixth preset time is 60-90 min.
In the implementation process, appropriate reaction raw materials are selected and reacted at an appropriate reaction temperature, so that the subsequent seed crystal and InP-based alloy quantum dot generation can achieve an optimal rate reaction, the size of the seed crystal is more uniform, and the efficiency and stability of the quantum dot are further improved.
In a second aspect, examples of the present application provide an InP quantum dot obtained by the method for preparing an InP quantum dot provided in the first aspect of the present application.
In the implementation process, the InP quantum dots have a core-shell structure, and the ZnSe/ZnS passivation shell layer covers the surface of the InP-based alloy quantum dots. The InP-based alloy quantum dots are provided with the transition layers with slowly-reduced lattice parameters, so that the InP-based alloy quantum dots can be matched with ZnSe/ZnS passivation shells with lower lattice parameters, and the InP-based alloy quantum dots have higher stability and quantum efficiency.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments or the prior art of the present application, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a flow chart of the preparation of InP quantum dots provided by examples of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of InP quantum dots and a method for preparing the same in the embodiments of the present application:
quantum dots, also known as fluorescent semiconductor nanocrystals, have significant quantum size effects that exhibit unique electronic and optical properties. The InP quantum dots do not contain heavy metal elements, the toxicity is far less than that of a II-VI family Cd class quantum dot material, the glass radius of the InP quantum dots is about 10nm (the block bandwidth is 1.35eV), the effective control of an emission peak from blue light (460nm) to near infrared light (750 nm) can be realized by adjusting the size of the quantum dots, and the InP quantum dots are an ideal nanometer material for replacing the Cd class quantum dots. And the InP quantum dots are direct band gap semiconductors and have high dielectric constants. Due to the unique properties of InP quantum dots, the InP quantum dots are widely applied to the fields of optical communication, detection, light-emitting diodes, biological imaging and the like.
However, because InP quantum dots have high covalency, many surface defects of core quantum dots are generated, the efficiency of quantum dots is low, and an effective passivation shell layer is generally required to be coated on the surface of the InP quantum dots to improve the quantum efficiency and stability of the InP quantum dots. At present, for InP quantum dots, ZnS or ZnSe/ZnS passivated shells are mainly used as the passivated shells.
However, the inventors found that the quantum efficiency of the InP quantum dots prepared in the prior art and coated with a passivated shell layer is low, and the practical application of the InP quantum dots is still limited.
Based on the above, the inventors provide a preparation method of an InP quantum dot to solve the problem of low quantum efficiency of an InP quantum dot coated with a passivated shell.
Referring to fig. 1, fig. 1 is a flow chart illustrating a method for fabricating InP quantum dots according to an example of the present application, where the method for fabricating InP quantum dots includes:
s1, mixing the InP seed crystal and the first Zn-In precursor, then performing first curing, adding the first phosphorus source, and performing second curing to obtain a first reactant; wherein the molar ratio of the first phosphorus source to In the first Zn-In precursor is 1: 0.8-4.
Illustratively, the molar ratio of the first phosphorus source to In the first Zn-In precursor includes, but is not limited to, a range between one or any two of 1:0.8, 1:0.9, 1:2, 1:3, and 1: 4.
In a possible embodiment, the molar ratio of the first phosphorus source to In the first Zn-In precursor is 1: 1.5-2.5, so as to avoid that the injection amount of the first phosphorus source is too small, the quantum dots cannot grow sufficiently, and the indium content of the quantum dots is increased, which leads to poor optical performance of the quantum dots, or the growth of the quantum dots tends to a disordered state due to too much injection amount of the first phosphorus source, which reduces the uniformity of the size of the quantum dots.
The present application does not limit how the InP seed crystals are obtained, and in one possible embodiment, the InP seed crystals are prepared by:
under an inert atmosphere, keeping the temperature of a mixture of a fourth phosphorus source, a second ligand and a cation (indium ion) precursor at a third preset temperature for a third preset time, and then heating to a fourth preset temperature to obtain InP crystal seeds;
wherein the molar ratio of the fourth phosphorus source to In the cationic precursor is 1: 1-5, wherein the molar ratio of In the cation precursor to the second ligand is 1:0.8 to 8; the third preset temperature is 30-250 ℃, the third preset time is 5min, and the fourth preset temperature is 230 ℃.
Illustratively, the molar ratio of the fourth phosphorus source to In the cationic precursor is In a range including, but not limited to, 1:1. 1:1.5, 1: 2. 1:4 and 1:5, or a range between any two. Illustratively, the molar ratio of In the cationic precursor to the second ligand is 1:0.8, 1:0.9, 1: 2. 1:6 and 1:8, or a range between any two.
Illustratively, the third predetermined temperature includes, but is not limited to, a range between one or any two of 30 ℃, 40 ℃, 100 ℃, 200 ℃ and 250 ℃.
In one possible embodiment, the fourth phosphorus source: the molar ratio of In the cationic precursor is 1: and 2, the molar ratio of In the cation precursor to the second ligand is 1: 2.
the present example does not limit the specific selection of the fourth phosphorus source, the second ligand, and the cationic precursor. In some possible embodiments, the fourth phosphorus source is selected from one or more of tris (trimethylsilyl) phosphorus, tris (triethylsilyl) phosphorus, tris (triphenylsilyl) phosphorus, tris (dimethylamino) phosphorus, tris (diethylamino) phosphorus; the second ligand is one or more selected from oleylamine, trioctylamine, trioctylphosphine, tributylphosphine, triphenylphosphine, dioctylamine, octylamine, dodecylamine and hexadecylamine.
In one possible embodiment, the cationic precursor may be obtained by the following preparation method:
under an inert atmosphere, mixing the components according to a molar ratio of 1: heating the first indium source and the first ligand which are configured by 0.5-8 to a second preset temperature and keeping the temperature for a second preset time; the second preset temperature is 120-260 ℃, and the second preset time is 30-180 min.
Illustratively, the first indium source: the molar ratio of the first ligand includes, but is not limited to, 1:0.5, 1:0.9, 1: 2. 1:6 and 1:8, or a range between any two. The second preset temperature includes but is not limited to a range between one or any two of 120 ℃, 130 ℃, 200 ℃, 220 ℃ and 260 ℃, and the second preset time includes but is not limited to a range between one or any two of 30min, 60min, 100min, 150min and 180 min.
In one possible embodiment, the molar ratio of 1:2, heating the first indium source and the first ligand to 200-260 ℃, and preserving heat for 60-90 min.
The present example does not limit the specific selection of the first indium source and first ligand, and the relevant person may make appropriate adjustments to ensure that the first indium source and first ligand are capable of forming a cationic precursor for reaction with the phosphorus source to form InP seeds.
In some possible embodiments, the first indium source is In 3+ Salt species including, but not limited to, one or more of indium acetate, indium nitrate, indium acetylacetonate, indium chloride, and indium sulfate. The first ligand is a saturated or unsaturated fatty acid with the carbon atom being more than or equal to 6, and comprises one or more of palmitic acid, oleic acid, myristic acid, palmitic acid, lauric acid and stearic acid; the fatty acid has a great influence on the quality of the InP quantum dots, and the fatty acid not only can enable the subsequent seed crystal generation to obtain the optimal rate reaction, but also can enable the size of the seed crystal to be uniform.
In order to further promote the uniformity and synthesis efficiency of the InP crystal seeds prepared by the cationic precursor obtained by the method in the subsequent reaction, the preparation process of the cationic precursor further comprises an acid discharge operation:
heating a first indium source and a first ligand which are configured according to a molar ratio to a second preset temperature, preserving heat for a second preset time, simultaneously discharging acid gas, cooling to a fifth preset temperature after preserving heat for the second preset time, adjusting the atmosphere state to be vacuum, and preserving heat for a fifth preset time; the fifth preset temperature is 100-180 ℃, and the fifth preset time is 30-180 min.
Acid gas is firstly removed in the reaction process at higher temperature, then the temperature is reduced, the atmosphere state is adjusted to be vacuum, the residual acid gas is further removed by utilizing the vacuumizing performed when the vacuum state is adjusted, and the generated reactant can be prevented from being discharged when the acid gas is removed by vacuumizing because the temperature during the vacuumizing is lower.
The application does not limit how the acid discharging operation is carried out, and in a possible embodiment, the acid gas can be discharged by arranging an exhaust system, and then the inert gas space where the reaction system is located is vacuumized by using a vacuum pump, so that the residual acid gas which is not discharged by the exhaust system is discharged.
The application does not limit how the first Zn-In precursor is obtained, and In one possible embodiment, the first Zn-In precursor is prepared by:
and under an inert atmosphere, heating a mixture of a second indium source, a zinc source, a third ligand and a non-coordinating solvent to a second preset temperature for a second preset time, wherein the molar ratio of the second indium source to the third ligand is 1: 0.5-8, and the molar ratio of the second indium source to the zinc source is 1: 0.2-10.
Illustratively, the second indium source: the molar ratio of the third ligand includes, but is not limited to, a range between one or any two of 1:0.5, 1:1, 1:4, 1:6, and 1: 8; illustratively, the second indium source: the molar ratio of the zinc source includes, but is not limited to, a range between one or any two of 1:0.2, 1:1, 1:4, 1:7, and 1: 10.
In one possible embodiment, the mixture of the second indium source, the third ligand and the zinc source in a molar ratio of 1:3:1 is heated to 200 to 240 ℃ for 60 to 90min under an inert atmosphere, such as an argon atmosphere.
The specific selection of the second indium source, the zinc source, the third ligand and the non-coordinating solvent is not limited In the application, and relevant personnel can correspondingly adjust the lattice parameters of the InP seed crystal by ensuring that the first Zn-In precursor can form indium-rich quantum dots with the InP seed crystal and react with the first phosphorus source added later to generate InP-based alloy quantum dots to reduce the lattice parameters of the InP seed crystal.
In some possible embodiments, the second indium source may be arbitrarily selected within a selection range of the first indium source, and the second indium source may be different from the first indium source. The third ligand may be arbitrarily selected within the selection range of the first ligand, and the third ligand may be different from the first ligand. The non-coordinating solvent may be selected from octadecene.
Also, In order to further promote the uniformity and synthesis efficiency of InP-based alloy quantum dots prepared using the first Zn-In precursor obtained by the above preparation method In a subsequent reaction, an acid discharge operation is further included In the preparation of the first Zn-In precursor, which is different from the acid discharge operation performed In the preparation of the cationic precursor In that: after the corresponding raw materials are kept warm for a second preset time, the temperature is reduced to a sixth preset temperature, the atmosphere state is adjusted to be vacuum, and the temperature is kept for a sixth preset time; the sixth preset temperature is 100-150 ℃, and the sixth preset time is 30-180 min.
Since the non-coordinating solvent, such as octadecene, added In the preparation process of the first Zn-In precursor has a certain volatility compared with other raw materials, the highest selectable temperature of the sixth preset temperature when the vacuum state is adjusted is relatively lower than the highest selectable temperature of the fifth preset temperature.
In one possible embodiment, the InP seed crystal may be heated to a first predetermined temperature of 210-260 ℃ and then kept for a first predetermined time of 10-60 min, so that the InP seed crystal system reaches a stable state, and the subsequent growth of the InP-based alloy quantum dots is facilitated. And then adding a first Zn-In precursor and mixing the stabilized InP seed crystal system.
Illustratively, the first preset temperature includes, but is not limited to, a range between one or any two of 210 ℃, 220 ℃, 235 ℃, 255 ℃, and 260 ℃. The first preset time includes, but is not limited to, a range between one or any two of 10min, 20min, 35min, 55min, and 60 min.
In one possible embodiment, the first predetermined temperature is 200-240 ℃, so that the InP seed crystal system is more stable.
And performing first curing to form the indium-rich quantum dots, and adding the first phosphorus source and then performing second curing to enable the first phosphorus source and the indium-rich quantum dots to react to generate the InP-based alloy quantum dots. The temperature and curing time of the first curing and the second curing are not limited in the application, and relevant personnel can adjust the temperature and curing time according to needs.
In some possible embodiments, the temperature of the first and second aging are each independently selected from one or a range between any two of 210 ℃, 230 ℃, 250 ℃, 260 ℃ and 280 ℃. The temperature of the first aging and the second aging may be the same.
The time of the first ripening and the second ripening may be different. For example, the first curing time is 10 to 60min, and the second curing time is 3 to 40 min.
S2, mixing the first reactant with a second Zn-In precursor, then carrying out third curing, adding a second phosphorus source, and carrying out fourth curing to obtain a second reactant; the second reactant contains InP-based alloy quantum dots, and the molar ratio of the second phosphorus source to In the second Zn-In precursor is 1: 0.8-4;
wherein the molar concentration of Zn In the first Zn-In precursor is less than the molar concentration of Zn In the second Zn-In precursor.
And (3) adding a Zn-In precursor for the second time, wherein the molar concentration of Zn In the second Zn-In precursor added In the step (2) is higher than that of Zn In the first Zn-In precursor added In the step (1), so that the alloy quantum dots with lower lattice parameters can be continuously grown outside the InP-based alloy quantum dots obtained In the step (1).
The preparation of the second Zn-In precursor In step (2) may refer to the preparation method In step (1), the third aging, the second phosphorus source, and the fourth aging In step (2) may refer to step (1), the second phosphorus source may be different from the first phosphorus source, and the temperature and time of the third aging and the fourth aging may be the same.
The application does not limit the addition of Zn-In precursors with different Zn molar concentrations for several times In the preparation process of InP quantum dots, and related personnel can correspondingly adjust the Zn-In precursors according to the needs. In one possible embodiment, in order to further reduce the lattice parameter of the InP-based alloy quantum dots to facilitate fitting to a ZnSe/ZnS passivated shell with a lower lattice parameter, the preparation of the InP quantum dots further comprises:
mixing the second reactant obtained In the step (2) with a third Zn-In precursor, performing fifth curing, adding a third phosphorus source, and performing sixth curing to obtain a third reactant; the third reactant contains InP-based alloy quantum dots, and the molar ratio of the third phosphorus source to In the third Zn-In precursor is 1: 0.8-4. And the molar concentration of Zn In the third Zn-In precursor is greater than that of Zn In the second Zn-In precursor In the step (2).
Similarly, In order to further slowly reduce the lattice parameter of the InP-based alloy quantum dot, a fourth Zn-In precursor, a fifth Zn-In precursor, a sixth Zn-In precursor, and the like may be further added step by step In such a manner that the molar concentration of Zn is increased gradually.
The method does not limit the difference of the molar concentration of Zn In the two Zn-In precursors added In the two adjacent steps, and related personnel can correspondingly adjust the molar concentration according to the requirements. In one possible embodiment, the second indium source is adjusted according to the preparation method of the first Zn-In precursor: the molar ratio of the zinc source is 1:0.5, 1:1, 1:3, 1:5, 1:7 and 1:10, so as to obtain a first Zn-In precursor, a second Zn-In precursor, a third Zn-In precursor, a fourth Zn-In precursor, a fifth Zn-In precursor and a sixth Zn-In precursor.
And S3, mixing and reacting the reactant containing the InP-based alloy quantum dots with the Zn precursor, the Se precursor and the S precursor to coat ZnSe/ZnS shell layers on the InP-based alloy quantum dots to form the InP quantum dots.
According to the method, how reactants containing the InP-based alloy quantum dots are mixed with the Zn precursor, the Se precursor and the S precursor and react is not limited, in one possible implementation mode, the Zn precursor and the InP-based alloy quantum dots are mixed, then a mixed system formed after mixing is heated to 180-340 ℃, and then the Se precursor and the S precursor are added.
The present application does not limit how the Zn precursor, Se precursor, and S precursor are obtained, and in one possible embodiment, the Zn precursor includes, but is not limited to, one or both of zinc acetate or zinc oleate, the Se precursor includes, but is not limited to, one or more of Se-TOP (tri-n-octylphosphine), Se-TBP (tributylphosphate), and Se-ODE (octadecene), and the S precursor includes, but is not limited to, one or more of S-TOP, S-TBP, and S-ODE.
In an example, the InP quantum dot prepared by the preparation method is also provided. The ZnSe/ZnS passivation shell layer in the InP quantum dots is coated on the surface of the InP-based alloy quantum dots, the InP-based alloy quantum dots comprise InP crystal nucleuses and at least two alloy quantum dot transition layers with lattice parameters gradually reduced from the inner layer to the surface layer, and the lattice parameters of the alloy quantum dot transition layer on the outermost layer are smaller than those of the alloy quantum dot transition layer close to the InP crystal nucleuses.
The InP quantum dots of the present application are further described in detail with reference to examples below.
Example 1
This example 1 provides an InP quantum dot prepared according to the following preparation method:
first step, preparation of InP seed crystals
0.6mmol of indium acetate and 1.8mmol of PA (phosphatidic acid) were weighed into a 50ml three-necked flask, which was kept under an Ar atmosphere, and heated to 240 ℃ with a heating mantle for 20 min. And then cooling to 180 ℃, changing an exhaust system into a vacuum system, and keeping for 30min to obtain the cation precursor. Then the temperature is reduced to 170 ℃, 0.30mmol TMS3P (tri (trimethylsilyl) phosphorus) and 1ml tri-n-octylphosphine TOP are injected rapidly to react for 5min, and then the temperature is raised to 230 ℃ and kept for 10min, finally the InP seed crystal is obtained.
Second step, preparation of Zn-In precursor
Weighing 3mmol of indium acetate, 1.5mmol of zinc acetate, 9mmol of PA and 15ml of octadecene, placing the materials In a 50ml three-neck flask, keeping the three-neck flask under the atmosphere of Ar, heating the materials to 240 ℃ by using a heating sleeve, keeping the temperature for 60min, then cooling the materials to 140 ℃, changing an exhaust system into a vacuum system, keeping the vacuum system for 60min, and finally obtaining a first Zn-In precursor;
the addition amount of zinc acetate is respectively adjusted to be 3.0mmol, 4.5mmol and 4.5mmol, and other conditions are not changed, so that a second Zn-In precursor, a third Zn-In precursor and a fourth Zn-In precursor are obtained.
Thirdly, preparing InP-based alloy quantum dots
And (2) placing the InP seed crystal obtained In the first step into a 100ml three-neck flask, heating to 230 ℃, keeping the temperature for 30min, injecting 1ml of the first Zn-In precursor obtained In the second step, curing at 230 ℃ for 20min, injecting 0.1mmol of TMS3P, and curing at 230 ℃ for 15 min. Injecting 1ml of the second Zn-In precursor obtained In the second step, curing at 230 ℃ for 20min, injecting 0.1mmol of TMS3P, and curing at 230 ℃ for 15 min. And the steps are alternately carried out, so that the addition of the third Zn-In precursor and the phosphorus source and the addition of the fourth Zn-In precursor and the phosphorus source are completed, and finally the InP-based alloy quantum dot is obtained.
Fourthly, preparation of ZnSe/ZnS shell layer
And adding 3.5mmol of zinc oleate and 7mmol of oleylamine into the InP-based alloy quantum dots obtained in the third step, heating to 310 ℃, and adding 0.8mmol of Se-tri-n-octylphosphine and 0.4mmol of S-tri-n-octylphosphine to finally obtain the InP quantum dots with ZnSe/ZnS coated on the InP-based alloy quantum dots.
Comparative example 1
Comparative example 1 differs from example 1 in that: in the third step, the InP seed crystal obtained In the first step and 0.4mmol TMS3P (namely, 0.1mmol first phosphorus source, 0.1mmol second phosphorus source, 0.1mmol third phosphorus source and 0.1mmol fourth phosphorus source are added at one time) are placed In a 100ml three-neck flask, the temperature is raised to 230 ℃ and kept for 30min, then 1ml first Zn-In precursor is injected, and the aging is carried out for 15min at 230 ℃; then injecting 1ml of second Zn-In precursor, and curing for 15min at 230 ℃; then injecting 1ml of third Zn-In precursor, and curing for 15min at 230 ℃; finally, 1ml of second Zn-In precursor is injected, and the mixture is cured for 15min at 230 ℃.
Comparative example 2
Comparative example 2 differs from example 1 in that:
and thirdly, placing the InP seed crystal obtained In the first step into a 100ml three-neck flask, heating to 230 ℃, keeping the temperature for 30min, then injecting 1ml of a first Zn-In precursor, curing at 230 ℃ for 20min, then injecting 0.1mmol of TMS3P, and curing at 230 ℃ for 15min to obtain the InP-based alloy quantum dot.
Fourthly, preparation of ZnSe/ZnS shell layer
And adding 3.5mmol of zinc oleate and 7mmol of oleylamine into the InP-based alloy quantum dots obtained in the third step, heating to 310 ℃, and adding 0.8mmol of Se-tri-n-octylphosphine and 0.4mmol of S-tri-n-octylphosphine to finally obtain the InP quantum dots coated with ZnSe/ZnS.
Experimental example 1
The quantum dots obtained in example 1, comparative example 1 and comparative example 2 were subjected to spectral and quantum efficiency tests. The life T95 indicates: time when the brightness decayed 95%. The test results are shown in table 1.
TABLE 1
| PL position/nm | PL half-Peak Width/nm | Service life T95/h | Quantum efficiency | |
| Example 1 | 530 | 29 | 340 | 12％ |
| Comparative example 1 | 530 | 34 | 180 | 6.5％ |
| Comparative example 2 | 530 | 31 | 200 | 8％ |
And (4) analyzing results: as can be seen from Table 1, the InP quantum dots prepared in example 1 of the present application have a PL half-peak width of 30nm or less and uniform quantum dot particle size. The InP quantum dots provided by the embodiment 1 have higher quantum dot efficiency and longer service life.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A preparation method of InP quantum dots is characterized by comprising the following steps:
(1) mixing InP crystal seeds and a first Zn-In precursor, then performing first curing, adding a first phosphorus source, and performing second curing to obtain a first reactant; wherein the molar ratio of the first phosphorus source to In the first Zn-In precursor is 1: 0.8-4;
(2) mixing the first reactant with a second Zn-In precursor, then carrying out third curing, adding a second phosphorus source, and carrying out fourth curing to obtain a second reactant; the second reactant contains InP-based alloy quantum dots, and the molar ratio of the second phosphorus source to In the second Zn-In precursor is 1: 0.8-4;
wherein the molar concentration of Zn In the first Zn-In precursor is less than the molar concentration of Zn In the second Zn-In precursor;
(3) and mixing and reacting reactants containing the InP-based alloy quantum dots with a Zn precursor, a Se precursor and an S precursor to coat ZnSe/ZnS shell layers on the InP-based alloy quantum dots to form the InP quantum dots.
2. The method for preparing InP quantum dots according to claim 1, wherein after (2) and before (3), the method further comprises:
mixing the second reactant with a third Zn-In precursor, performing fifth curing, adding a third phosphorus source, and performing sixth curing to obtain a third reactant; the third reactant contains InP-based alloy quantum dots, and the molar ratio of the third phosphorus source to In the third Zn-In precursor is 1: 0.8-4;
the molar concentration of Zn In the third Zn-In precursor is greater than the molar concentration of Zn In the second Zn-In precursor.
3. The method according to claim 2, wherein In the step (1), the first Zn-In precursor is added after the InP seed crystal is heated to a first predetermined temperature and kept at the temperature for a first predetermined time; the first preset temperature is 210-260 ℃, and the first preset time is 10-60 min;
the temperature of the first curing, the second curing, the third curing, the fourth curing, the fifth curing and the sixth curing is any temperature in the range of 210-280 ℃.
4. The method for preparing InP quantum dots according to claim 3, wherein the InP seed crystal is prepared by:
preparation of the cationic precursor:
under an inert atmosphere, mixing the raw materials according to a molar ratio of 1: heating the first indium source and the first ligand which are configured by 0.5-8 to a second preset temperature and keeping the temperature for a second preset time; the second preset temperature is 120-260 ℃, and the second preset time is 30-180 min;
preferably, the first indium source: the molar ratio of the first ligand is 1: 2;
preparing seed crystals:
under an inert atmosphere, keeping the temperature of a mixture of a fourth phosphorus source, a second ligand and the cation precursor at a third preset temperature for a third preset time, and then heating to a fourth preset temperature to obtain the InP seed crystal;
wherein the molar ratio of the fourth phosphorus source to In the cationic precursor is 1: 1-5, wherein the molar ratio of In the cationic precursor to the second ligand is 1:0.8 to 8;
preferably, the fourth phosphorus source: the molar ratio of In the cationic precursor is 1: 2;
preferably, the ratio of In: the molar ratio of the second ligand is 1: 2;
the third preset temperature is 30-250 ℃, the third preset time is 5min, and the fourth preset temperature is 230 ℃.
5. The method of claim 4, wherein the first Zn-In precursor comprises:
in an inert atmosphere, heating a mixture of a second indium source, a zinc source, a third ligand and a non-coordinating solvent to a second preset temperature, and preserving heat for a second preset time, wherein the molar ratio of the second indium source to the third ligand is 1: 0.5-8, and the molar ratio of the second indium source to the zinc source is 1: 0.2-10;
preferably, the second indium source: the molar ratio of the third ligand is 1: 3;
according to the preparation method of the first Zn-In precursor, the molar concentration of the zinc source is adjusted within the range that the molar ratio of the second indium source to the zinc source is 1: 0.2-10 so as to respectively obtain a second Zn-In precursor and a third Zn-In precursor;
preferably, according to the preparation method of the first Zn-In precursor, the second indium source is adjusted: the molar ratio of the zinc source is 1:1, 1:5, and 1:10 to obtain the first, second, and third Zn-In precursors.
6. The method of claim 5, wherein the preparation of the cationic precursor further comprises an acid removal operation:
keeping the temperature at the second preset temperature for the second preset time, and removing acid gas generated by the reaction; after the second preset time of heat preservation, cooling to a fifth preset temperature, adjusting the atmosphere state to be vacuum, and preserving heat for a fifth preset time; the fifth preset temperature is 100-180 ℃, and the fifth preset time is 30-180 min;
and/or the preparation method of the first Zn-In precursor further comprises an acid discharge operation:
keeping the temperature at the second preset temperature for the second preset time, and removing acid gas generated by the reaction; after the second preset time of heat preservation, cooling to a sixth preset temperature, adjusting the atmosphere state to be vacuum, and preserving heat for a sixth preset time; the sixth preset temperature is 100-150 ℃, and the sixth preset time is 30-180 min.
7. The method for preparing InP quantum dots according to claim 6, wherein the preparation of the ZnSe/ZnS shell layer further comprises:
and heating a mixed system formed by the Zn precursor and the InP-based alloy quantum dots to 180-340 ℃, and then adding the Se precursor and the S precursor.
8. The method of claim 7, wherein the first and second indium sources are In 3+ A salt species; optionally, the first indium source and the second indium source are each selected from one or more of indium acetate, indium nitrate, indium acetylacetonate, indium chloride and indium sulfate;
the first ligand and the third ligand are both saturated or unsaturated fatty acid with carbon atoms more than or equal to 6; optionally, the first ligand and the third ligand are each selected from one or more of palmitic acid, oleic acid, myristic acid, palmitic acid, lauric acid, and stearic acid;
the first phosphorus source, the second phosphorus source, the third phosphorus source and the fourth phosphorus source are all selected from one or more of tris (trimethylsilyl) phosphorus, tris (triethylsilyl) phosphorus, tris (triphenylsilyl) phosphorus, tris (dimethylamino) phosphorus and tris (diethylamino) phosphorus;
the second ligand is selected from one or more of oleylamine, trioctylamine, trioctylphosphine, tributylphosphine, triphenylphosphine, dioctylamine, octylamine, dodecylamine and hexadecylamine;
the zinc source is selected from Zn 2+ A salt species; optionally, the zinc source is at least one of zinc acetate, zinc chloride, and zinc stearate;
the non-coordinating solvent comprises octadecene.
9. The method for preparing InP quantum dots according to claim 8, wherein the first predetermined temperature is 220-240 ℃ and the first predetermined time is 20-40 min;
and/or the second preset temperature is 200-240 ℃, and the second preset time is 60-90 min;
and/or the third preset temperature is 130-170 ℃, and the third preset time is 5 min;
and/or the fifth preset temperature is 150-180 ℃, and the fifth preset time is 60-90 min;
and/or the sixth preset temperature is 120-130 ℃, and the sixth preset time is 60-90 min.
10. An InP quantum dot prepared by the method of any one of claims 1 to 9.
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