CN102976288A - New method for induced synthesis of nano-crystals through using inorganic complex of Sn (IV) - Google Patents

New method for induced synthesis of nano-crystals through using inorganic complex of Sn (IV) Download PDF

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CN102976288A
CN102976288A CN2012104351084A CN201210435108A CN102976288A CN 102976288 A CN102976288 A CN 102976288A CN 2012104351084 A CN2012104351084 A CN 2012104351084A CN 201210435108 A CN201210435108 A CN 201210435108A CN 102976288 A CN102976288 A CN 102976288A
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nanocrystalline
inorganic
size
synthetic
assembly behavior
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李林松
李晓民
申怀彬
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Henan University
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Henan University
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Abstract

The invention relates to a new method for the induced synthesis of nano-crystals with the morphology, the dimension and the assembling behavior being controllable through using an inorganic complex of Sn (IV). The method comprises the following steps: reacting an Sn (IV) salt which is a raw material with an excess pure dodecyl mercaptan or selenium solution to generate an Sn (IV) complex, and adopting the solution of the Sn (IV) complex as a reaction precursor to synthesize the nano-crystals with the morphology, the dimension and the assembling behavior being controllable. The method has the advantages of cheap and easily-available raw material, and simple experiment operation. For example, Cu2S and Cu2-xSe nano-crystals obtained through taking Cu2S and Cu2-xSe as raw materials are hexagonal sheets, and the hexagonal sheets can be assembled in a large area manner to form one-dimensional to three-dimensional cylindrical structures. The introduction of the inorganic complex enables the electrical conductivity of the synthesized semiconductor nano-crystals to be greatly improved. The method has very values in the laboratory research field or industrial application field based on the above characteristics.

Description

A kind of inorganic complexes with Sn (IV) is induced the novel method of synthesizing nanocrystalline
Technical field
The invention belongs to technical field of nano material, relate to a kind of inorganic complexes with Sn (IV) and induce the controlled nanocrystalline novel method of synthetic pattern, size and assembly behavior.The raw materials used cheapness of present method, be easy to get, experimental implementation is simple.With Cu 2S, Cu 2-xSe is example, synthetic gained Cu 2S and Cu 2-xSe is nanocrystalline to have large-area one dimension to three-dimensional packaging assembly, and the physical parameter such as its specific conductivity improves a lot without the title complex induction system.Therefore the present invention's very high value of tool all aspect laboratory study or industrial application.
Background technology
Semi-conductor nano particles, all has broad application prospects at aspects such as optoelectronic function device and biomedicines such as quantum size effect, Dielectric confinement effect and surface effects etc. owing to its special physics and chemistry character.Recent two decades comes, synthetic have obtained a lot of achievements aspect the semiconductor nano that size is controlled, pattern is controlled and composition is controlled.Along with the development of synthetic technology, design and construct and have the nanocrystalline of Special Sequence Structures and all attract wide attention in fundamental research and Applied research fields, and the basis will be provided for the exploitation of new nano material and nano-device.For realizing constructing of ordered structure, the technology such as self-assembly are widely adopted with its unique advantage.Organism tensio-active agent (such as oleic acid, oleyl amine etc.) is controlling factor comparatively crucial in the self-assembling technique, but because the insulation characterisitic of these long-chain organic systems, the material electrology characteristic that finally obtains is usually relatively poor, and this has also limited its application aspect nano-device.Recently, Talapin group finds that some inorganic complexes are such as (Sn 2S 6) 4-, (Sn 2Se 6) 4-Deng can coming the decorated nanometer particle and improve its stability as coating materials, in addition, the method by ion-exchange can also realize effective replacement that the inorganic surfaces promoting agent is modified organic surface active agent in nanoparticle surface.Principal feature of the present invention is the finishing of nanoparticle to be realized the control of pattern, size and self-assembly behavior to nanoparticle by inorganic part.The present invention is based on above viewpoint, realize first inorganic part induced nano crystals growth, and realized the Effective Regulation to nanocrystalline pattern, size and self-assembly behavior.
Summary of the invention
But the object of the present invention is to provide a kind of simple efficient, low-cost, good reproducibility and the synthetic inorganic part induced nano growth techniques of scale, and realize regulation and control to nanocrystalline pattern, size and self-assembly behavior with this, and optimize its electrology characteristic.
The technical solution used in the present invention is as follows:
In order to achieve the above object, it is the presoma of inorganic part that the present invention adopts the tetravalent metal pink salt, by being heated to 150-240 ℃ (under nitrogen environment) with the solution of excessive alkyl sulfhydryl or selenium is mixed, reaction certain hour (10-30 minute) generates the title complex of Sn-X, then take this title complex as reaction soln, by introduce needing therein the nanocrystalline presoma of preparation, synthetic pattern and size are controlled and have the nanocrystalline of good assembling performance under the certain temperature condition.
Wherein alkyl sulfhydryl can be lauryl mercaptan, and it is one of following that tetradecyl mercaptan etc., the solution of selenium are selected from: the octadecylene solution of selenium, benzene selenol etc.Wherein the nanocrystalline presoma of required preparation comprises, acetylacetone copper, copper stearate, cupric oleate, neutralized verdigris, capric acid copper, lauric acid copper, tetradecanoic acid copper, copper palmitate, methyl ethyl diketone silver, methyl ethyl diketone lead etc.
The present invention has following advantage with respect to prior art:
The employed raw material of present method is economic ep-type material, building-up process is simply efficient, good reproducibility, prepared nanocrystalline be inorganic material coating, has good assembly behavior, and greatly having strengthened conductive capability, therefore is the synthetic or industrial synthetic larger using value that all has in the laboratory.
Description of drawings
Fig. 1. the sheet hexagon Cu of big area one dimension assembling under the different amplification 2The Electronic Speculum picture that S is nanocrystalline.
Fig. 2. (A) (B) (C) (D) be respectively the sheet hexagon Cu of the different sizes that the differential responses time obtains 2The Electronic Speculum picture that S is nanocrystalline.(E) sheet hexagon Cu 2The nanocrystalline size of S is the curve over time of the distance between two sheets.
Fig. 3. the sheet hexagon Cu of large-area three-dimensional assembling under the different amplification 2The Electronic Speculum picture that S is nanocrystalline.
The sheet hexagon Cu that obtains when Fig. 4 .(A) not having the tetravalent metal pink salt to introduce 2-xSe is nanocrystalline; (B) the sheet hexagon Cu with self-assembly behavior of the complex decorating of Sn (IV) 2-xSe is nanocrystalline; (C) (D) sheet hexagon Cu 2The high-resolution electron microscopy picture that S is nanocrystalline.
Fig. 5. under the same conditions, the spherical Cu that lauryl mercaptan is modified 2The sheet hexagon Cu with self-assembly behavior of the complex decorating of the nanocrystalline and Sn (IV) of S 2The I-V graphic representation that S is nanocrystalline.
Fig. 6. do not use under the same conditions the complex decorating of Sn (IV) and the complex decorating Cu of use Sn (IV) 2-xThe I-V graphic representation that Se is nanocrystalline.
Embodiment
Embodiment 1
Synthetic sheet hexagon Cu with one dimension packaging assembly 2S is nanocrystalline: 0.0524 g (0.2 mmol) Cu (acac) 2, 0.0388 g (0.1mmol) Sn (acac) 2Cl 2And 5 after the mL lauryl mercaptan mixes, and is mixed and heated to 200 under nitrogen protection OCAnd kept 1 hour.The gained reaction product is the sheet hexagon Cu with one dimension assembling after being cooled to room temperature 2S is nanocrystalline.Shape appearance figure as shown in Figure 1.
Embodiment 2
Synthetic sheet hexagon Cu with three-dimensional group assembling structure 2S is nanocrystalline: 0.0388 g (0.1mmol) Sn (acac) 2Cl 2After mixing with 5 mL lauryl mercaptans, Hybrid Heating 200 under nitrogen protection OCObtain clarifying the solution of the title complex of Sn (IV).Be cooled to room temperature, then in this solution, add 0.0524 g (0.2 mmol) Cu (acac) 2, reheat to 200 after under nitrogen protection, mixing OCAnd kept 1 hour, the change of size situation that the different time sampling obtains in the reaction process is as shown in Figure 2.The gained reaction product is the sheet hexagon Cu with three-dimensional assembling after being cooled to room temperature 2S nanocrystalline (such as Fig. 3) solution.The nanocrystalline I-V Character Comparison figure that the I-V characteristic that its rear gained of purifying is nanocrystalline and use lauryl mercaptan coat as shown in Figure 5.
Embodiment 3
Synthesizing flaky hexagon Cu 2-xThe nanocrystalline sheet hexagon Cu with having three-dimensional assembling of Se 2-xSe is nanocrystalline: 0.125g(0.2mmol) copper stearate, and 0.6mmol oleic acid, 1.2mmol oil ammonia and 6 mL octadecylenes are mixed to join in the 50 mL three-necked bottles and are heated to gradually 200 under nitrogen environments oC, and keep 1h, obtain hexagon sheet Cu 2-xSe nanocrystalline (such as Fig. 4 A): synthetic Cu with three-dimensional assembling 2-xSe is nanocrystalline: 0.0388 g (0.1mmol) Sn (acac) 2Cl 2After mixing with 10 mL selenium solutions (selenium is dissolved into octadecylene the inside, and concentration is 0.1M), Hybrid Heating 200 under nitrogen protection OCObtain clarifying the solution of the title complex of Sn (IV).Be cooled to room temperature, then in this solution, add 0.125 g (0.2 mmol) Cu (St) 2, 0.6mmol oleic acid, 1.2mmol oil ammonia mix under nitrogen protection and reheat to 200 OCAnd kept 1 hour.Be cooled to room temperature gained reaction solution and be the sheet hexagon Cu with three-dimensional assembling 2-xSe nanocrystalline (such as Fig. 4 B).Do not add and add the prepared Cu of title complex of Sn (IV) 2-xThe nanocrystalline I-V curve comparison of Se as shown in Figure 6.

Claims (7)

  1. With the inorganic complexes of Sn (IV) as inducing the controlled nanocrystalline novel method of synthetic pattern, size and assembly behavior under the tensio-active agent condition, its characteristics are: the various inorganic complexes of Sn (IV) are dissolved in the organic solvent as inorganic surfaces promoting agent precursor, and are nanocrystalline or add the synthetic nanocrystalline pattern of nanocrystalline realization, size and self-assembly behavior control by directly add the required precursor synthesis of synthesizing nanocrystalline in the inorganic surfaces promoting agent precursor of above-mentioned preparation.
  2. 2. induce the controlled nanocrystalline method of synthetic pattern, size and assembly behavior according to claims 1 are described with inorganic complexes, wherein inorganic complexes comprises inorganic part that Sn, In, Ge, Ga etc. form etc., for example: Sn 2S 6 4-, Sn 2Se 6 4-, Sn 2Te 6 4-, In 2Se 6 4-Deng.
  3. 3. induce the controlled nanocrystalline method of synthetic pattern, size and assembly behavior according to claims 1 are described with inorganic complexes, the solvent that its characteristics are to form this inorganic ligand surface promoting agent is the organic solvent that contains excessive Se or S element, such as the octadecylene solution of lauryl mercaptan, Se, the whiteruss solution of Se etc.
  4. 4. induce the controlled nanocrystalline method of synthetic pattern, size and assembly behavior according to claims 1 are described with inorganic complexes, its characteristics are to form the temperature of this inorganic ligand surface promoting agent at 20-300 ℃.
  5. 5. induce the controlled nanocrystalline method of synthetic pattern, size and assembly behavior according to claims 1 are described with inorganic complexes, its characteristics are that the required presoma of synthesizing nanocrystalline that adds comprises the organic salt presoma of various metals in the inorganic surfaces activator solution that forms, such as Cu, Ag, Au, Zn, Cd, Pb, Pt, the organic slat solution of Pd etc.
  6. 6. induce the controlled nanocrystalline method of synthetic pattern, size and assembly behavior according to claims 1 are described with inorganic complexes, synthetic nanocrystalline comprising of adding in the inorganic surfaces activator solution that its characteristics are to form: monobasic, binary, ternary and polynary nanometer are brilliant, as Cu, Ag, Au, Pt, etc. monobasic nanocrystalline; Cu 2S, Cu 2-xSe, Cu 2-xThe bielement nanos such as Te, PbS, PbSe, PbTe, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, InP are brilliant; Zn xCd 1-xS, Zn xCd 1-xSe, CuInSe 2, CuInS 2, etc. ternary nanocrystals, and CuGa xIn 1-xS 2, CuGa xIn 1-xSe 2, Cu 2ZnSnSe 4, Cu 2ZnSnS 4Brilliant Deng polynary nanometer.
  7. 7. induce the controlled nanocrystalline method of synthetic pattern, size and assembly behavior according to claims 1 described inorganic complexes with Sn (IV), the inorganic complexes that its characteristics are Sn (IV) etc. can be regulated and control nanocrystalline pattern, size and assembly behavior in the middle of synthetic nanocrystalline.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103341638A (en) * 2013-07-10 2013-10-09 吉林大学 Method for assembling metal nanometer clusters of lamellar structure or structure similar to bipyramidal in high boiling point solvents
CN106670498A (en) * 2016-12-13 2017-05-17 中国海洋大学 Preparation method for copper-indium-tellurium ultrathin regular semiconductor nanosheets
CN108933257A (en) * 2018-08-31 2018-12-04 浙江大学 Cu as lithium ion battery electrode material2-xSe nano material and preparation method thereof
CN109777400A (en) * 2019-01-28 2019-05-21 山东师范大学 A kind of nontoxic Cu2S/ZnS core shell quantum dots and preparation method thereof
CN109880624A (en) * 2019-04-18 2019-06-14 武汉理工大学 The preparation method of microminiature PbSe quantum dot
CN110759374A (en) * 2019-12-06 2020-02-07 浙江工业大学 Cu2-xMorphology regulation and control method for S nanocrystal

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李晓民: "以乙酰丙酮金属盐为前驱体可控合成无机磁性、金属以及半导体纳米晶", 《中国优秀硕士学位论文全文数据库（工程科技I辑）》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103341638A (en) * 2013-07-10 2013-10-09 吉林大学 Method for assembling metal nanometer clusters of lamellar structure or structure similar to bipyramidal in high boiling point solvents
CN106670498A (en) * 2016-12-13 2017-05-17 中国海洋大学 Preparation method for copper-indium-tellurium ultrathin regular semiconductor nanosheets
CN108933257A (en) * 2018-08-31 2018-12-04 浙江大学 Cu as lithium ion battery electrode material2-xSe nano material and preparation method thereof
CN109777400A (en) * 2019-01-28 2019-05-21 山东师范大学 A kind of nontoxic Cu2S/ZnS core shell quantum dots and preparation method thereof
CN109777400B (en) * 2019-01-28 2022-02-08 山东师范大学 Non-toxic Cu2S/ZnS core/shell quantum dot and preparation method thereof
CN109880624A (en) * 2019-04-18 2019-06-14 武汉理工大学 The preparation method of microminiature PbSe quantum dot
CN109880624B (en) * 2019-04-18 2020-07-10 武汉理工大学 Preparation method of subminiature PbSe quantum dot
CN110759374A (en) * 2019-12-06 2020-02-07 浙江工业大学 Cu2-xMorphology regulation and control method for S nanocrystal

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Application publication date: 20130320