CN1304524C - Process for preparating ZnX (X=S, Se, Te) quantum point - Google Patents
Process for preparating ZnX (X=S, Se, Te) quantum point Download PDFInfo
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- CN1304524C CN1304524C CNB2004100046181A CN200410004618A CN1304524C CN 1304524 C CN1304524 C CN 1304524C CN B2004100046181 A CNB2004100046181 A CN B2004100046181A CN 200410004618 A CN200410004618 A CN 200410004618A CN 1304524 C CN1304524 C CN 1304524C
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 25
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 24
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title description 10
- 239000002096 quantum dot Substances 0.000 claims abstract description 73
- 239000000843 powder Substances 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000006184 cosolvent Substances 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 46
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 33
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 23
- 229910007709 ZnTe Inorganic materials 0.000 claims description 19
- 150000003003 phosphines Chemical class 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 235000021355 Stearic acid Nutrition 0.000 claims description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 14
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000008117 stearic acid Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- -1 fatty acid ester Chemical class 0.000 claims description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 150000002632 lipids Chemical class 0.000 claims description 6
- 229940033355 lauric acid Drugs 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229960003237 betaine Drugs 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 3
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical class PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 claims description 3
- 229920013701 VORANOL™ Polymers 0.000 claims description 2
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- SZLZWPPUNLXJEA-QEGASFHISA-N rescinnamine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)\C=C\C1=CC(OC)=C(OC)C(OC)=C1 SZLZWPPUNLXJEA-QEGASFHISA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 4
- 238000000576 coating method Methods 0.000 claims 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims 4
- 239000011669 selenium Substances 0.000 claims 3
- NGPLKXZXQSCKSN-UHFFFAOYSA-N P.[S] Chemical compound P.[S] NGPLKXZXQSCKSN-UHFFFAOYSA-N 0.000 claims 2
- XRHFHISEKQBHIN-UHFFFAOYSA-N [Se].P Chemical compound [Se].P XRHFHISEKQBHIN-UHFFFAOYSA-N 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000002994 raw material Substances 0.000 claims 2
- IYMSVBDSTPPHKQ-UHFFFAOYSA-M CCCCCCCCCCCCCCCCCC(=O)O[Zn] Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Zn] IYMSVBDSTPPHKQ-UHFFFAOYSA-M 0.000 claims 1
- XLSSMZDMEABLIO-UHFFFAOYSA-N octadecanoic acid;selenium Chemical compound [Se].CCCCCCCCCCCCCCCCCC(O)=O XLSSMZDMEABLIO-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 238000005424 photoluminescence Methods 0.000 description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000002105 nanoparticle Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000009102 absorption Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000103 photoluminescence spectrum Methods 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 5
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- FOCYCDUBYPKKDP-UHFFFAOYSA-N C(C)[Zn]CCCC.[Zn] Chemical compound C(C)[Zn]CCCC.[Zn] FOCYCDUBYPKKDP-UHFFFAOYSA-N 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a preparation method for a ZnX quantum dot (wherein X is selected from a kin group composed of S, Se, Te and a composition of S, Se and Te). The present invention has the following steps that the S powder, the Se powder and the Te powder or the composition of S, Se and Te are firstly added in organic alkali, and the S powder, the Se powder, the Te powder, or the composition of S, Se and Te and the organic alkali are formed into a mismatched substance A through the shock of ultrasonic waves; in addition, ZnO is added in organic acid and a cosolvent, and the ZnO, the organic acid and the cosolvent are formed into a mismatched substance through heating; finally, the mismatched substance A and the mismatched substance are mixed, and the ZnX (X=S, Se, Te) quantum dot is obtained.
Description
Technical field
The invention relates to a kind of ZnX (X=S, Se, the Te) preparation method of quantum dot, and be particularly to be precursor with ZnO, to utilize high temperature nonaqueous phase method to synthesize ZnX (X=S, Se, Te) preparation method of quantum dot a kind of.
Background technology
ZnX (X=S, Se, Te) be II-VI family semiconductive luminescent materials, its energy gap is ZnTe (Eg=2.39eV), ZnSe (Eg=2.82eV), ZnS (Eg=3.68eV), approximately between UV-light-visible light, and after mixing, can adjust its emission wavelength to the emission wavelength of being wished to get, and its luminous efficiency is good, so be phosphor material powder commonly used.
Conventional fluorescent powder synthesis mode is mostly at high temperature, as yttrium aluminum garnet (Yttrium AluminumGarnet, YAG), its general synthesis temperature is more than 1000 ℃, but because this extreme temperatures, crystal grain has the growth phenomenon, so size of particles is difficult to reach nano-scale (referring to that particle diameter is less than 100nm), more leisure opinion forms quantum dot (quantum dots refers to that particle diameter is less than 10nm).
Prove by Theoretical Calculation and international literature, quantum dot has the higher luminous efficiency of more traditional bulk, and can control energy gap and emission wavelength by size, can reduce usage quantity and save cost, and single-material can be realized full-color, so recent quantum dot fluorescence powder is various countries' science and technology research and development emphasis.
General ZnX (X=S, Se, Te) preparation method of quantum dot is for all at water, as ZnS, method commonly used at room temperature slowly adds sodium sulfide solution for salt such as the zinc nitrate with zinc is dissolved in the aqueous solution that contains interfacial agent, can form Zinc sulfide nano-particle, but the crystallinity of the nanoparticle of the synthetic gained of method is not good thus, and defective is many, and luminous is unsatisfactory.Chang Yong hydrothermal method at high temperature also can prepare sulfide nano-particle in addition, but bigger by the prepared nanoparticle particle of hydrothermal method, and size distribution is wide, and luminosity is also not good.
Over nearly 10 years, synthetic with nonaqueous phase, gradually become main flow at high temperature (about 200-400 ℃) synthesizing inorganic nanoparticle, 1998 Christian eras, Margaret A.Hines and Philippe Guyot-Sionnest are at the volume 102 of The Journal of Physical Chemistry B, number 19, among one piece of Bright UV-Blue Luminescent Colloidal ZnSe Nanocrystals by name, exposure with zinc ethyl (diethyl zinc) as precursor, add hexadecylamine (hexadecylamine, be called for short HDA), three hot phosphine (trioctylphosphine, be called for short TOP) and the Se powder, under about 310 ℃ of high temperature, make zinc ethyl and TOP-Se reaction, obtained nano level ZnSe quantum dot, the prepared ZnSe quantum dot of method crystallinity height thus, luminous efficiency is good, and particle distribution is extremely narrow, for preparing at present ZnSe or ZnTe quantum dot method commonly used.But regrettably, that the precursors-zinc ethyl of its use (diethyl zinc) has is inflammable, explosive, shortcoming such as cost an arm and a leg, and is not suitable for volume production.
Because ZnX (X=S, Se, the more popular research direction of the fluorescent material of Te) luminescent material great commercial value, and nano-scale even quantum dot grade, thus safety again the ZnX of economy (X=S, Se, Te) quantum dot the preparation method be an important research project.
Summary of the invention
In view of this, purpose of the present invention just is to provide a kind of ZnX (Te) preparation method of quantum dot, this preparation method has safety and economic dispatch characteristics concurrently for X=S, Se.
For reaching above-mentioned purpose, ZnX of the present invention (X=S, Se, Te) preparation method of quantum dot utilizes high temperature nonaqueous phase method to synthesize ZnX (X=S, Se, Te) quantum dot, and replace danger and expensive zinc ethyl as precursor with the cheap again zinc oxide of safety.
At first, place vacuum environment to remove aqueous vapor S powder, Se powder, Te powder or its composition, and for avoiding airborne aqueous vapor and oxygen to make S powder, Se powder, Te powder or its composition humidity, rotten or oxidation, S powder, Se powder, Te powder or its composition of the gas that anhydrates are placed under the rare gas element, and adding organic bases, this organic bases is three hot phosphines, three fourth phosphines or three methylphosphines, and utilize ultrasonic oscillation to handle after 30 minutes, promptly form the misfit thing of S powder, Se powder, Te powder or its composition and this organic bases.
In addition ZnO is heated to 120 ℃ to remove adsorbed aqueous vapor under inert gas environment, adds organic acid (organic acid) and cosolvent (co-solvent) after cooling again, reheat makes ZnO, organic acid and cosolvent three form the misfit thing.
Above-mentioned organic acid can be the oxide compound (phosphine with lipophilic group oxides) of carboxylic acid,-sulfinic acid, lipid acid (aliphatic compounds), alkylphosphonic acid carboxylic acid (alkyl phosphonic acid), lipophilic phosphine (phosphine with lipophilicgroup) or lipophilic phosphine.Wherein carboxylic acid can be laurostearic acid, stearic acid or isocaproic acid; Lipid acid can be lipid acid (aliphaticacids), fatty acid ester (aliphatic acid esters), fatty acid alcohol (aliphatic alcohols) or lipid acid aldehyde (aliohatic aldehydes), as lauric acid (lauric acid, abbreviation LA), stearic acid (stearic acid, be called for short SA), m-phthalic acid (isophthalic acid is called for short IA) etc.; Alkylphosphonic acid carboxylic acid is hexamethyl phosphoric acid (hexyl-phosphonic acid is called for short HPA), phosphoric acid in four-last of the ten Heavenly stems (tetra-decylphosphonic acid is called for short TDPA) or phosphoric acid in eight-last of the ten Heavenly stems (octa-decylphosphonic acid is called for short ODPA).
Above-mentioned cosolvent can be oxide compound, organic amine, organic alcohol or other solvent of lipophilic phosphine, lipophilic phosphine.Wherein the lipophilic phosphine is three fourth phosphines (tri-butylphosphine is called for short TBP), three hot phosphines (tri-octylphosphine is called for short TOP) or three methylphosphines (tri-methylphosphine is called for short TMP); The lipophilic phosphine oxide is oxidation three hot phosphines (tri-octylphosphine oxide is called for short TOPO); Organic amine is an amine to three ten amine; Other solvent is Yelkin TTS (lecithin), N, N-dimethyl-N-alkyl-N-carboxyl methyl, N, N-dialkyl amino olefinic carboxylic acid salt, N, N, N-trialkyl-N-sulphur alkene betaine, N, N-dialkyl group-N, N-double focusing oxygen ethene sulfuric ester betaine or Voranol EP 2001.
At last with this two liquid mixed more than 120 ℃, promptly get ZnX (X=S, Se, Te) quantum dot.(Te) quantum dot is to synthesize in organic solution for X=S, Se owing to this ZnX, so formed ZnX (X=S, Se, Te) the quantum dot surface can be coated by these organic molecules naturally, forms the structure of nuclear and shell (core/shell), the existence of these organic molecule shells can completely cut off ectocine, as oxidation etc., make nuclear, just ZnX (X=S, Se, Te) character of quantum dot is more stable.
In addition, different elements can mix in this system, or use two or three X (wherein X selects from the group that S, Se, Te and its composition are formed) and adjust the various ratio of X, the lattice of ZnX quantum dot is changed, control its emission wavelength.
Description of drawings
Fig. 1 is a synoptic diagram, in order to ZnX of the present invention (X=S, Se, Te) quantum dot and organic molecular structure to be described.
Fig. 2 is the energy dispersed light spectrogram of a ZnSe quantum dot.
Fig. 3 is a ZnSe quantum dot and stearic X-ray diffraction chart.
Fig. 4 is the X-ray diffraction chart of a ZnSe quantum dot.
Fig. 5 is the transmission electron microscope photo of a ZnSe quantum dot.
Fig. 6 is the abosrption spectrogram of the ZnSe quantum dot of a differential responses time.
Fig. 7 is the photoluminescence spectrogram of the ZnSe quantum dot of a blue light-emitting.
Fig. 8 is a photoluminescence spectrogram of ZnSe quantum dot that turns blue green glow.
Fig. 9 is the photoluminescence spectrogram of the ZnSe quantum dot of a green light.
Figure 10 is the photoluminescence spectrogram of the ZnSe quantum dot of a jaundice light.
Figure 11 is the photoluminescence spectrogram of a ZnSe quantum dot that emits white light.
Figure 12 is the photoluminescence spectrogram of the ZnSe quantum dot of a differential responses time.
Figure 13 is the energy dispersed light spectrogram of a ZnS quantum dot.
Figure 14 is the transmission electron microscope photo of a ZnS quantum dot.
Figure 15 is the abosrption spectrogram of a ZnS quantum dot.
Figure 16 is the photoluminescence spectrogram of a ZnS quantum dot.
Figure 17 is the X-ray diffraction chart of a ZnTe quantum dot.
Figure 18 is the abosrption spectrogram of a ZnTe quantum dot.
Figure 19 is the photoluminescence spectrogram of a ZnTe quantum dot.
Figure 20 is the photoluminescence spectrogram of a ZnTe quantum dot that emits white light.
Nomenclature:
100～ZnX (X=S, Se, Te) quantum dot nuclear
200～organic molecule shell
Embodiment
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and cooperate appended graphicly, be described in detail below:
The preparation of embodiment 1---ZnSe and evaluation
The preparation of ZnSe
At first, place vacuum environment to remove the aqueous vapor of absorption in the Se powder of 0.3948 gram, and for avoiding airborne aqueous vapor and oxygen to make Se powder humidity, rotten or oxidation, the gas Se powder that will anhydrate places under the inert gas environment, and add 5 milliliter of three hot phosphine (tri-octylphosphine, be called for short TOP), and after ultrasonic oscillation is handled about 30 minutes, promptly form colourless TOPSe misfit thing liquid.
In addition, 0.81 gram ZnO powder is placed in the three-necked bottle, under inert gas environment, be heated to 120 ℃ to remove adsorbed aqueous vapor, to be cooled to room temperature, add 2 gram cetylamines (Hexadecylamine is called for short HDA) again, with 2 gram stearic acid (Stearic acid, be called for short SA), the above-mentioned medicine to 150 of reheat ℃ was held temperature 20 minutes, and this moment, reaction liquid was transparence.
Temperature is risen to 300 ℃ at last, add TOPSe liquid,, can generate the ZnSe nanoparticle that is of a size of 1～20nm by reaction times control; The particle diameter of ZnSe nanoparticle increased with the reaction times, and in the nano material characteristic, particle diameter is more little usually, and its energy gap is big more, shows that blue displacement (blue shift) phenomenon in the spectrum is obvious more.
The liquid that has reacted is faint yellow, and behind distillatory methanol/toluene purifying, product can be stored in the toluene.
The evaluation of ZnSe
Utilize energy scatter spectra (Enetgy Dispersive Spectrometer, abbreviation EDS), X-ray diffractometer (X-Ray Diffraction Meter, abbreviation XRD), transmission electron microscope (Transmission Electron Microscopy is called for short TEM), absorption spectrum and photoluminescence spectrum are identified the character of this sample.
Fig. 2 is the energy dispersed light spectrogram of sample, thus energy scatter spectra map analysis result as can be known sample composition comprise elements such as Zn, Se, C and P.
Fig. 3 is the X-ray diffraction chart of sample, thus X-ray diffraction chart analytical results as can be known sample comprise the diffraction peak of ZnSe diffraction peak and hard acid fat, prove ZnSe and stearic existence; If behind the stearic acid of hot methanol and ultrasonication removal ZnSe surface coverage, can get only ZnSe diffraction peak, as shown in Figure 4.
Fig. 5 is the transmission electron microscope photo of sample, and therefore the transmission electron microscope photo about 4nm of particle diameter of sample as can be known can be described as quantum dot thus; And the particle surface of good crystallinity is surrounded by the material of crystallinity difference, infers that this nuclear and the structure of shell are the organism of ZnSe crystallization outsourcing crystallinity difference.
Fig. 6 is the abosrption spectrogram of sample, is the sample of differential responses time and the relation of absorption spectrum among the figure, and absorption peak is positioned between 350～430nm, is typical ZnSe abosrption spectrogram; The result shows that the reaction times is short more, and absorbing wavelength is short more, conform with the reaction times short more, product cut size is more little, the tangible more inference of the blue offset phenomena of its spectrum.
Fig. 7 to Figure 11 is the photoluminescence spectrogram of ZnSe sample, this serial spectrogram is to utilize different precursorses to form, the ZnSe quantum dot sample of synthetic gained, and photoluminescence spectrum is between 400～700nm, be respectively blue light, blue green light, green glow, gold-tinted, and can get white light ZnSe quantum dot.
Figure 12 is the photoluminescence spectrogram of ZnSe sample, is the sample of differential responses time and photoluminescence spectrographic relation among the figure; The result shows that the reaction times is short more, and absorbing wavelength is short more, conform with the reaction times short more, product cut size is more little, the tangible more inference of the blue offset phenomena of its spectrum.
Comprehensive above qualification result can know the method for the present invention of utilizing, and can get the quantum dot of ZnSe really, and this quantum dot surface coats one deck organic substance; In addition, the different size quantum dot has different absorptions and radiation wavelength, and its absorption of quantum dot that size is more little is short more with the radiation wavelength; In addition, utilize different precursorses to form, also can obtain different the absorption and the quantum dot that radiates wavelength.
The preparation of embodiment 2---ZnS and evaluation
The preparation of ZnS
At first, place vacuum environment to remove the aqueous vapor of absorption in the sulphur powder of 0.0163 gram, and for avoiding airborne aqueous vapor and oxygen to make S powder humidity, rotten or oxidation, the gas S powder that will anhydrate places under the inert gas environment, and add 0.5 milliliter of three hot phosphine (tri-octylphosphine, be called for short TOP), and after ultrasonic oscillation is handled about 30 minutes, promptly form colourless TOPS misfit thing liquid.
In addition, 0.0405 gram ZnO powder is placed in the three-necked bottle, under inert gas environment, be heated to 120 ℃ to remove adsorbed aqueous vapor, to be cooled to room temperature, add 11.4 gram stearic acid (stearic acid is called for short SA) or 0.3673 gram oxidation, three hot phosphines (tri-octylphosphineoxide is called for short TOPO) again, the above-mentioned medicine to 150 of reheat ℃ was held temperature 20 minutes, and this moment, reaction liquid was transparence.
Be warming up to 300 ℃ at last, add TOPS misfit thing liquid again, generate the ZnS nanoparticle that is of a size of 1～20nm by the reaction times may command; The particle diameter of ZnS nanoparticle increased with the reaction times, and in the nano material characteristic, particle diameter is more little usually, and its energy gap is big more, shows that blue displacement (blue shift) phenomenon in the spectrum is obvious more.
The evaluation of ZnS
Utilize energy scatter spectra (Energy Dispersive Spectrometer, abbreviation EDS), transmission electron microscope (Transmission Electron Microscopy is called for short TEM), absorption spectrum and photoluminescence spectrum are identified the character of this sample.
Figure 13 is the energy dispersed light spectrogram of sample, thus energy scatter spectra map analysis result as can be known sample composition comprise elements such as Zn, S, C and P.
Figure 14 is the transmission electron microscope photo of sample, and therefore the transmission electron microscope photo about 4nm of particle diameter of sample as can be known can be described as quantum dot thus; And the particle surface of good crystallinity is surrounded by the material of crystallinity difference, infers that this nuclear and the structure of shell are the organism of ZnS crystallization outsourcing crystallinity difference.
Figure 15 is the abosrption spectrogram of sample, and absorption peak is positioned between 300～400nm, is typical ZnS abosrption spectrogram.
Figure 16 is the photoluminescence spectrogram of sample, is one to be positioned at wide radiation peak between 350～700nm, is the photoluminescence spectrum of typical ZnS.
Comprehensive above qualification result can know the method for the present invention of utilizing, and can get the quantum dot of ZnS really, and this quantum dot surface coats one deck organic substance.
The preparation of embodiment 3---ZnTe and evaluation
The preparation of ZnTe
At first, place vacuum environment to remove the aqueous vapor of absorption in the Te powder of 1.276 grams, and for avoiding airborne aqueous vapor and oxygen to make S powder humidity, rotten or oxidation, the gas S powder that will anhydrate places under the inert gas environment, and add 15 milliliters and go into three hot phosphines (tri-octylphosphine TOP), and after ultrasonic oscillation is handled about 30 minutes, promptly form green TOPTe misfit thing liquid.
In addition, 1.215 gram ZnO powders are placed in the three-necked bottle, under inert gas environment, be heated to 120 ℃ to remove adsorbed aqueous vapor, to be cooled to room temperature, add 1.0016 gram stearic acid (Lauric acid is called for short SA) and 23.2 gram oxidations, three hot phosphines (tri-octylphosphineoxide is called for short TOPO) again, the above-mentioned medicine to 150 of reheat ℃ was held temperature 20 minutes, and this moment, reaction liquid was transparence.
Be warming up to 300 ℃ at last, add TOPTe misfit thing liquid again, promptly generate the ZnTe nanoparticle that is of a size of 1～20nm; The particle diameter of ZnTe nanoparticle increased with the reaction times, and in the nano material characteristic, particle diameter is more little usually, and its energy gap is big more, shows that blue displacement (blueshift) phenomenon in the spectrum is obvious more.
The evaluation of ZnTe
Utilize X-ray diffractometer (X-Ray Diffraction Meter is called for short XRD), absorption spectrum and photoluminescence spectrum to identify the character of this sample.
Figure 17 is the X-ray diffraction chart of sample, thus X-ray diffraction chart analytical results as can be known sample comprise ZnTe diffraction peak, prove the existence of ZnTe.
Figure 18 is the abosrption spectrogram of sample, and absorption peak is positioned between 300～400nm, is typical ZnTe abosrption spectrogram.
Figure 19 is the photoluminescence spectrogram of sample, is one to be positioned at wide radiation peak between 350～700nm, is the photoluminescence spectrum of typical ZnTe.
Figure 20 is the photoluminescence spectrogram of sample, is one to be positioned at wide radiation peak between 350～750nm, is the photoluminescence spectrum of the ZnTe that emits white light.
Comprehensive above qualification result can know the method for the present invention of utilizing, and can get the quantum dot of ZnTe really.
Claims (13)
1. the preparation method of a ZnX quantum dot, wherein X selects from the group that S, Se, Te and its composition are formed, and comprises the following step:
(a) with making it dissolving in the raw material X adding organic bases, obtain one first misfit thing solution;
(b) ZnO is added make it in organic acid and the cosolvent dissolving, obtain one second misfit thing solution;
(c) the mixed above-mentioned first misfit thing solution and the second misfit thing solution promptly get surperficial ZnX quantum dot for the organic molecule coating.
2. the preparation method of ZnX quantum dot according to claim 1, wherein this raw material X selects from the group that S powder, Se powder, Te powder and its composition are formed.
3. the preparation method of ZnX quantum dot according to claim 1, wherein this organic bases is three hot phosphines, three fourth phosphines or three methylphosphines.
4. the preparation method of ZnX quantum dot according to claim 1, wherein this organic acid is the oxide compound of laurostearic acid, stearic acid, isocaproic acid,-sulfinic acid, lipid acid, fatty acid ester, fatty acid alcohol, lipid acid aldehyde, alkylphosphonic acid carboxylic acid, lipophilic phosphine or lipophilic phosphine.
5. the preparation method of ZnX quantum dot according to claim 4, wherein this alkylphosphonic acid carboxylic acid be hexamethyl phosphoric acid, four-last of the ten Heavenly stems phosphoric acid or eight-last of the ten Heavenly stems phosphoric acid.
6. the preparation method of ZnX quantum dot according to claim 1, wherein this cosolvent is oxide compound, organic amine, organic alcohol or other solvent of lipophilic phosphine, lipophilic phosphine.
7. the preparation method of ZnX quantum dot according to claim 6, wherein this lipophilic phosphine is three fourth phosphines or three hot phosphines.
8. the preparation method of ZnX quantum dot according to claim 6, wherein this lipophilic phosphine oxide is oxidation three hot phosphines.
9. the preparation method of ZnX quantum dot according to claim 6, wherein this organic amine is an amine to three ten amine.
10. the preparation method of ZnX quantum dot according to claim 6, wherein this other solvent is to select certainly in Yelkin TTS, N, N-dimethyl-N-alkyl-N-carboxyl methyl, N, N-dialkyl amino olefinic carboxylic acid salt, N, N, N-trialkyl-N-sulphur alkene betaine, N are in the group that N-dialkyl group-N, N-double focusing oxygen ethene sulfuric ester betaine and Voranol EP 2001 are formed.
11. the preparation method of a ZnS quantum dot comprises the following step:
(a) the S powder is added make it in the three hot phosphines dissolving, obtain one or three hot phosphine sulphur solution;
(b) ZnO is added make it in stearic acid and the oxidation three hot phosphines dissolving, obtain monostearate zinc and oxidation three hot phosphine solution;
(c) mixed above-mentioned three hot phosphine sulphur solution and Zinic stearas and oxidation three hot phosphine solution promptly get surperficial ZnS quantum dot for the organic molecule coating.
12. the preparation method of a ZnSe quantum dot comprises the following step:
(a) the Se powder is added make it in the three hot phosphines dissolving, obtain one or three hot phosphine selenium solutions;
(b) ZnO is added make it in stearic acid and the oxidation three hot phosphines dissolving, obtain monostearate selenium and oxidation three hot phosphine solution;
(c) mixed above-mentioned three hot phosphine selenium solutions and stearic acid selenium and oxidation three hot phosphine solution promptly get surperficial ZnSe quantum dot for the organic molecule coating.
13. the preparation method of a ZnTe quantum dot comprises the following step:
(a) the Te powder is added make it in the three hot phosphines dissolving, obtain one or three hot phosphine tellurium solution;
(b) ZnO is added make it in stearic acid and the oxidation three hot phosphines dissolving, obtain monostearate tellurium and oxidation three hot phosphine solution;
(c) mixed above-mentioned three hot phosphine tellurium solution and stearic acid tellurium and oxidation three hot phosphine solution promptly get surperficial ZnTe quantum dot for the organic molecule coating.
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| CN1328351C (en) * | 2005-09-23 | 2007-07-25 | 上海大学 | Method for preparing II-VI family fluorescent mark semiconductor quantum point MX |
| CN100567986C (en) * | 2005-12-22 | 2009-12-09 | 复旦大学 | The preparation method of a kind of water-soluble CdTe/CdS core/shell type quantum dot |
| CN100383216C (en) * | 2006-03-09 | 2008-04-23 | 复旦大学 | Prepn. process of ZnSe/ZnS kernel/shell type quantum points |
| CN103897702B (en) * | 2014-04-20 | 2015-08-05 | 吉林师范大学 | A kind of ZnSe quantum dot and preparation method thereof |
| CN103991850B (en) * | 2014-05-14 | 2016-10-26 | 新疆大学 | A kind of preparation method of the ZnTe of the S that adulterates |
| CN110581264B (en) * | 2019-08-28 | 2022-03-18 | 复旦大学 | High-performance nickel-zinc battery negative electrode active material and preparation method thereof |
| CN114981385B (en) * | 2020-12-25 | 2023-12-15 | 京东方科技集团股份有限公司 | Preparation method of ZnSe quantum dot, znSe structure and display device |
| CN114316950B (en) * | 2022-01-12 | 2022-08-26 | 广东粤港澳大湾区国家纳米科技创新研究院 | Method for preparing quantum dot material by precursor capsule, quantum dot material, quantum dot composition and quantum dot device |
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| CN1352207A (en) * | 2001-11-30 | 2002-06-05 | 中国科学院长春光学精密机械与物理研究所 | Process for preparing copper and aluminium blended zinc sulfide nanometer fluorescent powder in batchs |
| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
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| CN1352207A (en) * | 2001-11-30 | 2002-06-05 | 中国科学院长春光学精密机械与物理研究所 | Process for preparing copper and aluminium blended zinc sulfide nanometer fluorescent powder in batchs |
| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
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