CN101264868B - Method for preparing selenium-containing compound nano crystal - Google Patents
Method for preparing selenium-containing compound nano crystal Download PDFInfo
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- CN101264868B CN101264868B CN2008100493041A CN200810049304A CN101264868B CN 101264868 B CN101264868 B CN 101264868B CN 2008100493041 A CN2008100493041 A CN 2008100493041A CN 200810049304 A CN200810049304 A CN 200810049304A CN 101264868 B CN101264868 B CN 101264868B
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- cadmium
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 51
- 239000011669 selenium Substances 0.000 title claims abstract description 51
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 230000012010 growth Effects 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000003342 selenium Chemical class 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims description 12
- 150000001661 cadmium Chemical class 0.000 claims description 11
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 10
- -1 Zinic stearas Chemical compound 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 claims description 6
- 108091074834 12 family Proteins 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 claims description 3
- ZTSAVNXIUHXYOY-CVBJKYQLSA-L cadmium(2+);(z)-octadec-9-enoate Chemical compound [Cd+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O ZTSAVNXIUHXYOY-CVBJKYQLSA-L 0.000 claims description 3
- 229940098697 zinc laurate Drugs 0.000 claims description 3
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- ITQVEYJXZXMBTR-UHFFFAOYSA-L cadmium(2+);dodecanoate Chemical compound [Cd+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O ITQVEYJXZXMBTR-UHFFFAOYSA-L 0.000 claims description 2
- IIQMTDRLNJPBIP-UHFFFAOYSA-N cadmium;decanoic acid Chemical compound [Cd].CCCCCCCCCC(O)=O IIQMTDRLNJPBIP-UHFFFAOYSA-N 0.000 claims description 2
- CMZQABJYGBTXFW-UHFFFAOYSA-N cadmium;tetradecanoic acid Chemical compound [Cd].CCCCCCCCCCCCCC(O)=O CMZQABJYGBTXFW-UHFFFAOYSA-N 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- SDSLQTDGQCIMCU-UHFFFAOYSA-N decanoic acid;zinc Chemical compound [Zn].CCCCCCCCCC(O)=O SDSLQTDGQCIMCU-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 229940012185 zinc palmitate Drugs 0.000 claims description 2
- 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 claims description 2
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 claims description 2
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 21
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 125000003748 selenium group Chemical group *[Se]* 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 3
- 238000003786 synthesis reaction Methods 0.000 abstract 3
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 11
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 10
- 239000003086 colorant Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 6
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- 229910005543 GaSe Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- TYSIUBDGWQYTDK-UHFFFAOYSA-N cadmium;methane Chemical compound C.[Cd] TYSIUBDGWQYTDK-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- JRPGMCRJPQJYPE-UHFFFAOYSA-N zinc;carbanide Chemical compound [CH3-].[CH3-].[Zn+2] JRPGMCRJPQJYPE-UHFFFAOYSA-N 0.000 description 1
- IPSRAFUHLHIWAR-UHFFFAOYSA-N zinc;ethane Chemical group [Zn+2].[CH2-]C.[CH2-]C IPSRAFUHLHIWAR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a preparation method of selenium-bearing compound nanocrystal, which comprises following steps: heating the precursor of the twelve family elements to 240 to 380 DEG C in inertia environment; mixing with the selenium precursor at 20 to 300 DEG C; enabling the growth of the mixture at 240 to 380 DEG C for 1 to 12 hours to obtain the selenium-bearing compound nanocrystal; wherein, the selenium precursor is obtained by dissolving selenium salt in the solvent with additives; the additives are organic amine or organic acid with the carbon content of no less than 10; the solvent is non-coordinating solvent with the dissolving point of no more than 60 DEG C; the molar ratio of the additives and the selenium is 3 to 5:1. The method has the advantages of regular and stable low toxicity medicine for synthesis, economy, environmental friendliness, capability of saving cost of over 80%, high quality of nanocrystal, even size distribution, high fluorescence efficiency, narrow FWHM (full width at half maximum), and huge application value in both laboratory synthesis and industrial synthesis.
Description
(1) technical field
The present invention relates to a kind of preparation method of selenium-containing compound nano crystal, the method for the synthetic high quality selenium-containing compound nano crystal of particularly a kind of without phosphorus method.
(2) background technology
Semi-conductor nano particles, especially II-VI family semi-conductor nano particles is a hot research in recent years.Semi-conductor nano particles is also referred to as semiconductor-quantum-point (Quantum Dots, be called for short QDs), because its size is smaller, several to tens nanometer sizes, so can produce not available physics of many body materials and chemical property, as quantum size effect, dielectric confinement effect, surface effects etc., it is had broad application prospects at aspects such as optoelectronic equipment, solar cell, laser biology marks.Recently the research of visible light light-emitting zone semiconductor nano, the especially application as biomarker obtain paying close attention to.2000, Peng etc. found a kind of inorganic method synthesizing nanocrystalline, cheapness and toxicity relatively a little less than, promptly use Cadmium oxide (CdO) to replace methyl cadmium (Cd (CH
3)
2) synthetic CdSe is nanocrystalline and replace methyl zinc or the synthetic ZnSe of zinc ethyl nanocrystalline with Zinic stearas.Recently (trioctylphosphineoxide TOPO) as solvent, makes the synthesizing nanocrystalline cost further reduce to have the human octadecylene to replace trioctyl phosphine oxide.That yet Peng etc. and other group use when the presoma of synthetic selenium always is tributyl phosphorus (tributylphosphine, TBP) or tri octyl phosphine (trioctylphosphine, TOP) dissolved selenium is as the presoma of selenium, the shortcoming of this method is that tributyl phosphorus or tri octyl phosphine all are poisonous inflammable and explosive medicines, and costs an arm and a leg.The bright lock of Zou group in 2005 finds selenium powder is dissolved in the whiteruss, it is nanocrystalline that the method for injecting the cadmium precursor then when high temperature can be synthesized CdSe, yet institute's nanocrystalline quality of synthetic does not reach the effect when using tributyl phosphorus or tri octyl phosphine, and the method for the therefore without phosphorus synthetic high quality selenium-containing compound nano crystal of low cost still belongs to blank.
(3) summary of the invention
The method that the object of the present invention is to provide a kind of without phosphorus low cost to synthesize the high quality selenium-containing compound nano crystal, simple to operate, process is easy to control.
The technical solution used in the present invention is as follows:
A kind of preparation method of selenium-containing compound nano crystal, presoma with 12 family's elements under inert environments is heated to 240-380 ℃, be that the presoma of 20-300 ℃ of selenium mixes with temperature then, make mixture obtain selenium-containing compound nano crystal at 240-380 ℃ of growth 1s-12h, wherein the presoma of selenium prepares by selenium salt is dissolved in the solvent that contains additive, one of described additive is to contain carbon number to be not less than 10 organic amine or organic acid, preferred following: stearylamine, cetylamine, amino dodecane, oleyl amine, oleic acid, stearic acid; Described solvent is that molten point is not higher than 60 ℃ non-ligand solvent; Wherein in additive and the selenium salt amount of substance of selenium than being 3-5: 1.
Wherein, described 12 family's elements are preferably cadmium or zinc.The presoma of described 12 family's elements is preferably cadmium salt or zinc salt or both mixtures and acid or amine and is dissolved in the solution that molten point is not higher than 60 ℃ non-ligand solvent, and cadmium salt or zinc salt or both mixtures are 1 with the amount of substance ratio of acid or amine: 2-10.
Preferably, the above solvent is selected from the mixture of one of following or any several arbitrary proportions: octadecylene, 1-icosa alkene, tetracosane, mineral oil, whiteruss, paraffin or sweet oil.The amount of solvent is advisable can dissolve presoma.
Described cadmium salt can be selected soap or its inorganic salt of cadmium, preferred one of following or several mixture arbitrarily wherein: cadmium oleate, cadmium stearate, capric acid cadmium, cadmium laurate, tetradecanoic acid cadmium, palmitinic acid cadmium, Cadmium oxide or cadmium nitrate.Described zinc salt can be selected soap or its inorganic salt of zinc, is preferably one of following or several mixture arbitrarily wherein: zinc oleate, Zinic stearas, capric acid zinc, zinc laurate, Zinc tetradecanoate, zinc palmitate, zinc oxide.
Concrete, the amount that adds cadmium salt is a selenium and the amount of substance ratio of cadmium is 1: 0.1-2, the amount that adds zinc salt is a selenium and the amount of substance ratio of zinc is 1: 0.15-4.
The different speeds that come conditioned reaction of the kind that the inventive method can be by regulating additive or the amount of additive or implantation temperature and growth temperature, for example when additive is the amine organism along with the additive add-on increase the reaction slack-off, when additive is the acids organism along with the additive add-on increase the reaction accelerate; The selenium-containing compound nano crystal that makes is the point-like particle, and fluorescence quantum yield is greater than 60%, and size deviation is in 5%.The present invention uses cadmium salt and zinc salt nanocrystalline as synthetic CdSe of the precursor of cadmium and zinc and ZnSe, avoided use tributyl phosphorus or tri octyl phosphine dissolved selenium precursor simultaneously as selenium, no matter be that the precursor of selenium is injected in high temperature cadmium salt or the zinc solution in the process, still cadmium salt or zinc solution be injected into can obtain in the high temperature selenium solution high-quality nanocrystalline.The nanocrystalline halfwidth of synthetic CdSe between 20-50nm spectral range at 470-650nm, the nanocrystalline halfwidth of synthetic ZnSe between 14-40nm spectral range at 400-450nm.
The present invention has following advantage with respect to prior art:
Present method avoids using tributyl phosphorus or the tri octyl phosphine dissolved selenium precursor as selenium, economic environmental protection, what use in the building-up process all is the medicine of the stable low murder by poisoning of routine, and it is cost-saved more than 80%, obtain nanocrystalline and use TBP or TOP dissolved selenium nanocrystalline equal quality of synthetic during as the precursor of selenium, even size distribution, the fluorescence efficiency height, halfwidth is narrow.Present method also is applicable to synthetic PbSe, GaSe, CuInSe
2Etc. nanocrystalline, be the synthetic or industrial synthetic huge using value that all has in the laboratory.
(4) description of drawings
Fig. 1 is the nanocrystalline fluorescence spectrum figure of the CdSe of different size.
Fig. 2 is the nanocrystalline abosrption spectrogram of the CdSe of different size.
Fig. 3 is the nanocrystalline transmission electron microscope picture of CdSe.
Fig. 4 is the nanocrystalline fluorescence spectrum figure of different size ZnSe.
Fig. 5 is the nanocrystalline absorption spectrum collection of illustrative plates of ZnSe.
Fig. 6 is the transmission electron microscope picture of Mi Jing in the ZnSe.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
Get the 0.12mmol cadmium oleate, 0.24mmol stearylamine, 4g octadecylene mix puts into the 25mL three-necked bottle, is heated to 280 ℃ under the nitrogen environment up to the solution complete and homogeneous; 1.2mmolSe powder, 3.6mmol stearylamine and 10ml octadecylene are mixed the back in 220 ℃ of heating, obtain flaxen selenium precursor solution, get 2mL selenium precursor solution and inject three-necked bottle rapidly, then temperature is dropped to 260 ℃ of growths.Be colourless when solution has just injected, gradually become faint yellow, yellow, incarnadine, redness, scarlet, garnet then, the reaction times is three hours, and the CdSe that stops to obtain different size at solution during for different colours is nanocrystalline.The solution of different colours taken a sample respectively carry out the test of fluorescence spectrum and absorption spectrum, fluorescence peak changes to 650nm by 470nm.Fluorescence pattern such as Fig. 1 absorb collection of illustrative plates such as Fig. 2, transmission electron microscope picture such as Fig. 3 that wavelength 550nm is nanocrystalline.
Embodiment 2
Get the 0.12mmol Cadmium oxide, 0.3mmol oleic acid, 3.8g octadecylene mix puts into the 25mL three-necked bottle, is heated to 260 ℃ under the nitrogen environment up to the solution complete and homogeneous; 1.2mmolSe powder, 3.6mmol stearylamine and 10ml icosa alkene are mixed the back obtain flaxen selenium precursor solution, get 3mL selenium precursor solution and inject three-necked bottle rapidly, then temperature is dropped to 240 ℃ of growths in 220 ℃ of heating.Be colourless when solution has just injected, gradually become faint yellow, yellow, incarnadine, redness, scarlet, garnet then, the reaction times is two hours, and the CdSe that stops to obtain different size at solution during for different colours is nanocrystalline.The solution of different colours taken a sample respectively carry out fluorescence spectrum and absorb test, fluorescence peak changes to 620nm by 470nm.
Embodiment 3
Get the 0.12mmol cadmium stearate, 1.2mmol stearylamine, 5g tetracosane mix puts into the 25mL three-necked bottle, is heated to 240 ℃ under the nitrogen environment up to the solution complete and homogeneous; 1.2mmolSe powder, 3.6mmol oleic acid and 10ml whiteruss are mixed the back in 220 ℃ of heating, obtain flaxen selenium precursor solution, get 4mL selenium precursor solution and inject three-necked bottle rapidly, then temperature is dropped to 260 ℃ of growths.Be colourless when solution has just injected, gradually become faint yellow, yellow, incarnadine, redness, scarlet, garnet then, the reaction times is three hours, and the CdSe that stops to obtain different size at solution during for different colours is nanocrystalline.The solution of different colours taken a sample respectively carry out fluorescence spectrum and absorb test, fluorescence peak changes to 650nm by 470nm.
Embodiment 4
Get the 0.24mmol Zinic stearas, 0.74mmolg stearylamine, 3.7g whiteruss mix puts into the 25mL three-necked bottle, is heated to 330 ℃ under the nitrogen environment up to the solution complete and homogeneous.1.2mmol selenium powder, 3.6mmol stearylamine and 10ml octadecylene are mixed the back obtain faint yellow selenium precursor solution in 220 ℃ of heating, get 1mL selenium precursor solution and inject three-necked bottle rapidly, mixing solutions drops to 280 ℃ to temperature rapidly then and grows.The nanocrystalline fluorescent absorption collection of illustrative plates of different size ZnSe such as Fig. 4, nanocrystalline absorption collection of illustrative plates such as Fig. 5 of ZnSe that growth 30min obtains, the nanocrystalline transmission electron microscope picture of the ZnSe of wavelength 440nm such as Fig. 6.
Embodiment 5
Get 0.48mmol zinc oxide, 3mmol stearic acid, 8g whiteruss mix puts into the 50mL three-necked bottle, is heated to 330 ℃ under the nitrogen environment up to the solution complete and homogeneous.With after 1.2mmol selenium powder, 3.6mmol stearylamine and the 10ml mixed with olive oil in 220 ℃ of heating, obtain faint yellow selenium precursor solution, get 1mL selenium precursor solution and inject three-necked bottle rapidly, mixing solutions drops to 280 ℃ of growth 30min to temperature rapidly then, and synthetic ZnSe is nanocrystalline.
Embodiment 6
Get the 0.12mmol zinc laurate, 1.2mmol stearylamine, 4.0g icosa alkene mix puts into the 25mL three-necked bottle, is heated to 360 ℃ under the nitrogen environment up to the solution complete and homogeneous.1.2mmol selenium powder, 3.6mmol stearic acid and 10ml icosa alkene are mixed the back obtain faint yellow selenium precursor solution in 220 ℃ of heating, get 2mL selenium precursor solution and inject three-necked bottle rapidly, mixing solutions is adjusted to 330 ℃ of growth 15min to temperature then, and synthetic ZnSe is nanocrystalline.
Claims (3)
1. the preparation method of a selenium-containing compound nano crystal, it is characterized in that under the inert environments presoma of 12 family's elements is heated to 240-380 ℃, be that the presoma of 220-300 ℃ of selenium mixes with temperature then, make mixture obtain selenium-containing compound nano crystal at 240-380 ℃ of growth 1s-12h, wherein the presoma of selenium prepares by selenium salt is dissolved in the solvent that contains additive, described additive is one of following: stearylamine, cetylamine, amino dodecane, oleyl amine, oleic acid or stearic acid, wherein in additive and the selenium salt amount of substance of selenium than being 3-5: 1, described solvent is that molten point is not higher than 60 ℃ non-ligand solvent; The presoma of described 12 family's elements is that cadmium salt or zinc salt or both mixtures and acid or amine are dissolved in the solution that molten point is not higher than 60 ℃ non-ligand solvent, cadmium salt or zinc salt or both mixtures are 1 with the amount of substance ratio of acid or amine: 2-10, described cadmium salt is one of following or wherein any several mixtures: cadmium oleate, cadmium stearate, capric acid cadmium, cadmium laurate, tetradecanoic acid cadmium, palmitinic acid cadmium or cadmium nitrate, described zinc salt are one of following or wherein any several mixtures: zinc oleate, Zinic stearas, capric acid zinc, zinc laurate, Zinc tetradecanoate, zinc palmitate; Above-mentioned molten point is not higher than the mixture that 60 ℃ non-ligand solvent is selected from one of following or any several arbitrary proportions: octadecylene, 1-icosa alkene, tetracosane, mineral oil, paraffin, sweet oil.
2. the preparation method of selenium-containing compound nano crystal as claimed in claim 1, the amount that it is characterized in that adding cadmium salt are selenium and the amount of substance ratio of cadmium is 1: 0.1-2.
3. the preparation method of selenium-containing compound nano crystal as claimed in claim 1, the amount that it is characterized in that adding zinc salt are selenium and the amount of substance ratio of zinc is 1: 0.15-4.
Priority Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101554999B (en) * | 2009-04-30 | 2012-02-22 | 河南大学 | Method for synthesizing tellurium-contained semiconductor nanocrystal |
| CN101830445B (en) * | 2009-12-15 | 2014-12-10 | 河南大学 | Novel method for synthetizing inorganic nanocrystal by taking acetylacetone as raw material |
| CN101823702A (en) * | 2010-05-14 | 2010-09-08 | 中国科学院上海技术物理研究所 | Preparation method of Cu2CdSnSe4 nano crystals |
| CN102976289A (en) * | 2012-11-01 | 2013-03-20 | 河南大学 | New method for preparing semiconductor nano-crystals containing tellurium, selenium or sulfur |
| CN103130201B (en) * | 2013-02-22 | 2015-02-11 | 合肥京东方光电科技有限公司 | Zinc selenide fluorescent nano-particles and preparation method thereof |
| CN103275724B (en) * | 2013-05-31 | 2015-03-11 | 合肥京东方光电科技有限公司 | Preparation method of fluorescent nanoparticle |
| CN103361066A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for synthesizing CdSe/CdS core-shell structure quantum dots through one step |
| CN104692339A (en) * | 2014-07-28 | 2015-06-10 | 深圳丹邦投资集团有限公司 | Cu3SbSe3 nanometer material and preparation method of Cu3SbSe3 nanometer material |
| CN104692340A (en) * | 2014-07-28 | 2015-06-10 | 深圳丹邦投资集团有限公司 | Selenium precursor for preparing metal selenide nanometer material |
| CN104495762B (en) * | 2014-12-11 | 2018-01-19 | 深圳丹邦投资集团有限公司 | Nanocrystalline ZnSe preparation method, ZnSe be nanocrystalline and the preparation method of ZnSe cushions |
| CN105038798A (en) * | 2015-08-21 | 2015-11-11 | 清华大学 | Method for preparing cadmium selenide quantum dot |
| CN108795412B (en) * | 2017-06-15 | 2021-08-20 | 苏州星烁纳米科技有限公司 | Quantum dot and preparation method thereof |
| CN111604064A (en) * | 2020-05-12 | 2020-09-01 | 河南大学 | Pollution-free hydrothermal synthesis method of zinc selenide microspheres and synthesis method of composite material thereof |
| CN113060706B (en) * | 2021-03-23 | 2024-02-09 | 中国科学技术大学 | Preparation method of colloid ZnSe quantum wire with adjustable size |
| CN114196978B (en) * | 2021-11-17 | 2022-10-28 | 南京晓庄学院 | Preparation method and application of Ru-CdSe heterogeneous nanocrystal |
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