CN101901827B - Core/shell type wurtzite/blende ZnS hetero nano structure and preparation method thereof - Google Patents
Core/shell type wurtzite/blende ZnS hetero nano structure and preparation method thereof Download PDFInfo
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- CN101901827B CN101901827B CN2010102275458A CN201010227545A CN101901827B CN 101901827 B CN101901827 B CN 101901827B CN 2010102275458 A CN2010102275458 A CN 2010102275458A CN 201010227545 A CN201010227545 A CN 201010227545A CN 101901827 B CN101901827 B CN 101901827B
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- 229910052984 zinc sulfide Inorganic materials 0.000 title claims abstract description 128
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 32
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 claims description 41
- 229910000238 buergerite Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052950 sphalerite Inorganic materials 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000007323 disproportionation reaction Methods 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 3
- 230000018199 S phase Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 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 invention discloses a core/shell type wurtzite/blende ZnS hetero nano structure and a preparation method thereof. The hetero nano structure is formed in a way that hexagonal wurtzite ZnS particles of which the diameter is 100-300 nm are coated by a shell made of cubic blende ZnS nano particles of which the diameter is less than 10 nm. By using Zn(NO3)2.6H2O and elementary sulfur as raw materials and using ethanol and water as solvent, the preparation method comprises the following steps: making the raw materials and the solvent react in a teflon-lined stainless steel closed container, and synthesizing the core/shell type wurtzite/blende ZnS hetero nano structure by using disproportionation reaction of the elementary sulfur in an alkali medium, wherein the reaction temperature is 120-180 DEG C, the reaction time is 10-50 hours, and the mass of caustic soda is 1-5 times of that of Zn(NO3)2.6H2O. Under the conditions of not using any template and not adding any surfactant, the ratio of the wurtzite ZnS to the blende ZnS can be changed by adjusting the mol ratio of Zn to S. The invention has the advantages of simple process, low cost and easy process control.
Description
One, technical field
The present invention relates to core/shell type buergerite/zincblende ZnS hetero nano structure of a kind of novelty and preparation method thereof.
Two, background technology
ZnS has the performance of multiple excellence, has extensive use in various fields.ZnS is a kind of wide band gap semiconducter, is to remove AlN, and outside the MgS, the semiconductor that band gap is the wideest; The heterogeneous phonon that do not need in its electronics and hole is assisted, and luminous efficiency is high; And the exciton activation energy of ZnS is 40meV, and far above room temperature heat energy 26meV, the room-temperature exciton existence of having ready conditions can be implemented in the ZnS nano material of advantages of good crystallization and produces the room temperature excitonic luminescence; ZnS is the optimum substrate of powder electroluminescence up to now; Can be used for plasma and electroluminescence, flat panel display (like FED), cathode ray tube (being used for radar, TV and oscilloscope), transducer many fields such as (X-ray, Y-ray are surveyed); Also can be used for making photoelectricity (solar energy) senser, nano material laser is made and be used to make the laser coatings of the photoelectricity distinguishing mark of special wavelength control.ZnS also is a kind of infrared optical material, has higher infrared transmittivity and good light, machine, calorifics combination property at 3～5 μ m and 8～12 mu m wavebands, is best aircraft dual-band infrared watch window and hood material.In addition, the ZnS H stronger to the reproducibility of low concentration
2S gas has very high sensitivity, and antijamming capability is strong.
Zinc sulphide has two kinds of common crystal structures, i.e. the zincblende lattce structure of cube phase and six sides wurtzite structure mutually.In these two kinds of lattice structures, metallic zinc ion (Zn
2+) be in sulphion (S
2-) in the formed tetrahedron of the closs packing space, constitute ZnS4 coordination tetrahedron.These coordination tetrahedrons are formed the periodic network configuration of three dimensions through sharing mutual connection of summit.Although the coordination environment of two kinds of crystal structures is identical, because zinc ion has just occupied half the tetrahedron space, the difference of coordination tetrahedron on accumulation mode that causes has therefrom just produced different symmetry, has generated the crystals with different structure.Pure zincblende lattce structure changes wurtzite-type at 1020 ℃, but the existence of impurity can reduce transition temperature.In the disclosed documents and materials, study the synthetic and performance of single buergerite ZnS or zincblende ZnS mostly, the performance of the ZnS of research two-phase coexistent is also arranged, but the buergerite/heterogeneous nano material of zincblende ZnS with core/shell structure is not seen bibliographical information so far.
Three, summary of the invention
The objective of the invention is, propose a kind of core/shell type buergerite/zincblende ZnS hetero nano structure and preparation method thereof.
Core/shell type buergerite/zincblende ZnS hetero nano structure; It is characterized in that the hexagonal wurtzite ZnS particle with diameter 100～300 nanometers is a core; The outside shell of being formed less than the cubic zinc blende ZnS nano particle of 10 nanometers by diameter wraps up a kind of heterogeneous nano material of ZnS with core/shell structure of formation.
Technical scheme of the present invention is: core/shell type buergerite of the present invention/zincblende ZnS hetero nano structure preparation method: in stainless steel (inner liner polytetrafluoroethylene) closed container, with Zn (NO
3)
26H
2O and elemental sulfur raw material are to react in the solvent at the second alcohol and water, and utilize the disproportionated reaction of elemental sulfur in the highly basic medium to synthesize core/shell type buergerite/zincblende ZnS hetero nano structure; Reaction temperature is 120-180 ℃, and the reaction time is 10-50 hour, and the volume ratio of water and ethanol is 1: 4-1: 6, and the mol ratio of Zn and S is 5: 1-1: 1.The highly basic medium adopts caustic soda, and the quality of caustic soda is Zn (NO
3)
2 6H
21 to 5 times of the quality of O.
In the solvent of second alcohol and water, add proper ammonia in addition, the ammoniacal liquor quality is the 10-25% of the solvent of second alcohol and water, the concentration 15-25% of ammoniacal liquor.
The ratio of buergerite ZnS and zincblende ZnS can recently be regulated through the mole of Zn and S in the product that obtains.Mol ratio at Zn and S is 5: 1-1: in 1 scope; Can obtain core/shell type buergerite/zincblende ZnS hetero nano structure: core is the hexagonal wurtzite ZnS particle of diameter 100～300 nanometers, and shell is formed less than the cubic zinc blende ZnS nano particle of 10 nanometers by diameter.If the addition of sulphur is too much, have to zincblende ZnS nano particle.The present invention without any need for template, need not add under the situation of any surfactant and react.
Core/shell type buergerite/zincblende ZnS the hetero nano structure for preparing with method of the present invention; Have and conventional buergerite ZnS or zincblende ZnS different energy levels structure; Thereby show different optical properties; This core/shell type buergerite/zincblende ZnS hetero nano structure still has no bibliographical information so far.
Product with the present invention's preparation carries out structure and performance characterization through following means: the thing of product adopts the D/Max-RA type rotarting anode x-ray diffractometer (XRD) of Japanese Rigaku manufactured to analyze (CuKa) mutually; Sirion field emission scanning electron microscope (FE-SEM) and JEOL-2010 type high resolution transmission electron microscopy (HRTEM) that the pattern of product adopts JSM-5610LV type scanning electron microscopy (SEM), FEI Co. to produce characterize, and adopt He-Cd laser (excitation wavelength: 325nm) tested the photoluminescence spectrum (PL) of sample.
The invention has the beneficial effects as follows: propose a kind of core/shell type buergerite/zincblende ZnS hetero nano structure and preparation method thereof, utilize the disproportionated reaction of elemental sulfur in the highly basic medium to synthesize novel core/shell type buergerite/zincblende ZnS hetero nano structure.The present invention has that preparation technology is simple, cost is low, process is controlled easily, is easy to scale, environmental friendliness, characteristics such as pollution-free; Through regulating the mol ratio of Zn and S; Can change the ratio of buergerite ZnS and zincblende ZnS; And then change the exciton absworption peak of material and the position at luminescence generated by light peak, and make the heterogeneous nano material of synthetic ZnS have the optical property different with conventional ZnS, can be used for fields such as photocatalysis, transducer.Also can be used for sapecial coating etc.
Four, description of drawings
Fig. 1 is the transmission electron microscope photo of the product that obtains of embodiment 1, and can clearly observe core/shell structure: core is buergerite ZnS, about 200 nanometers of average diameter; Shell forms for the zincblende ZnS less than 10 nanometers piles up.
Fig. 2 is the field emission scanning electron microscope photo of the product that obtains of embodiment 1.Whole product is elliposoidal, and the outside is wrapped up by the particle less than 10 nanometers.
Fig. 3 is the X-ray diffraction spectrogram of product.Fig. 3 (a) is embodiment 1 sample; Fig. 3 (b) is embodiment 2 samples; Fig. 3 (c) is embodiment 3 samples.Can obviously observe two cover spectrograms from the X-ray diffraction spectrogram: more sharp-pointed (show crystal grain is very big, crystallization better) is six side's phase ZnS, is a cube phase ZnS than (little crystal grain causes and composes peak widthization) of broad change.Therefore can infer that synthetic product is to be core with six side's phase ZnS, shell is made up of the tiny cube ZnS of crystal grain.In addition, the mol ratio of Zn and S has material impact to the composition of product, if the addition of sulphur is too much, has to zincblende ZnS nano particle.
Five, embodiment
Below be embodiments of the invention (agents useful for same is a chemical pure among the embodiment).
Embodiment 1: at first with 14.87 gram Zn (NO
3)
26H
2O and 40.0 gram NaOH are dissolved in the deionized water, are mixed with 100 milliliters of clear solutions; Measure 3 milliliters of above-mentioned solution, being placed into volume and being 80 milliliters has in the teflon-lined stainless steel closed container, adds 5.0 ml deionized water again, 25.0 milliliters of absolute ethyl alcohols; Mol ratio according to Zn and S is 3: 1 then, adds the S powder; The stainless steel closed container of screwing; Be placed into the stainless steel closed container in the baking oven, 150 ℃ are incubated 24 hours.After naturally cooling to room temperature, open reactor, obtain solid product.With the solid product centrifugation, water and ethanol respectively clean and obtain core/shell type buergerite/heterogeneous nano material of zincblende ZnS for 3 times.
With above-mentioned condition; In ethanolic solution, add 5.0 milliliters of ammonia spirits (concentration is 25%); Effect is roughly the same above-mentioned; As shown in Figure 1, can clearly observe core/shell structure: core is that the shell that buergerite ZnS (diameter is the hexagonal wurtzite ZnS particle of 100～300 nanometers) is formed less than the cubic zinc blende ZnS nano particle of 10 nanometers by diameter is wrapped up the heterogeneous nano material of the ZnS with core/shell structure of formation.
Other condition is constant, adopts the result of 30.0 gram NaOH constant.
Other condition is constant, and reaction temperature is 150-180 ℃, and the reaction time is that 15-24 hour result is all constant, and time lengthening does not have significant change yet.
Embodiment 2: compare with embodiment 1 (interpolation ammoniacal liquor), the quality that difference is to add S is 3 times of embodiment 1, and the mol ratio that makes Zn and S is 1: 1, and all the other conditions are all identical in embodiment 1.The composition of product is seen accompanying drawing 2 (b), and the composition of zincblende ZnS is obviously than embodiment more than 1 in the core/shell type that obtains buergerite/heterogeneous nano material of zincblende ZnS.
Embodiment 3: compare with embodiment 1 (interpolation ammoniacal liquor), the quality that difference is to add S is 9 times of embodiment 1, and the mol ratio that makes Zn and S is 1: 3, and all the other conditions are all identical in embodiment 1.The composition of product is seen accompanying drawing 2 (3), and the product that obtains mainly is zincblende ZnS, does not obtain core/shell type buergerite/heterogeneous nano material of zincblende ZnS, and the mol ratio that shows Zn and S has material impact to the composition of end product.
Embodiment 4: compare (interpolation ammoniacal liquor) with embodiment 1, and 180 ℃ of difference reaction temperatures, the reaction time is 18 hours, all the other conditions are all identical in embodiment 1.The core/shell type buergerite that the obtains/heterogeneous nano material of zincblende ZnS, about 300 nanometers of the average diameter of core buergerite ZnS; The average diameter of zincblende ZnS nano particle is about 10 nanometers in the shell.
Claims (4)
1. core/shell type buergerite/zincblende ZnS hetero nano structure; It is characterized in that the shell that diameter is formed less than the cubic zinc blende ZnS nano particle of 10 nanometers by diameter by the hexagonal wurtzite ZnS particle of 100 ~ 300 nanometers is wrapped up the heterogeneous nano material of the ZnS with core/shell structure of formation.
2. the preparation method of core/shell type buergerite/zincblende ZnS hetero nano structure is characterized in that in inner liner polytetrafluoroethylene stainless steel closed container, with Zn (NO
3)
26H
2O and elemental sulfur raw material are to react in the solvent at the second alcohol and water, and utilize the disproportionated reaction of elemental sulfur in the highly basic medium to synthesize core/shell type buergerite/zincblende ZnS hetero nano structure; Reaction temperature is 120-180
oC, the reaction time is 10-50 hour, and the volume ratio of water and ethanol is 1:4-1:6, and the mol ratio of Zn and S is 5:1-1:1; The highly basic medium adopts caustic soda, and the quality of caustic soda is Zn (NO
3)
26H
21 to 5 times of the quality of O.
3. the preparation method of core/shell type buergerite according to claim 2/zincblende ZnS hetero nano structure is characterized in that in the solvent of second alcohol and water, adding proper ammonia, and the ammoniacal liquor quality is the 10-25% of the solvent of second alcohol and water, the concentration 15-25% of ammoniacal liquor.
4. the preparation method of core/shell type buergerite according to claim 2/zincblende ZnS hetero nano structure; The ratio of buergerite ZnS and zincblende ZnS is recently regulated through the mole of Zn and S in the product that it is characterized in that obtaining: the mol ratio at Zn and S is in the 5:1-1:1 scope; Obtain core/shell type buergerite/zincblende ZnS hetero nano structure: core is the hexagonal wurtzite ZnS particle of diameter 100 ~ 300 nanometers, and shell is formed less than the cubic zinc blende ZnS nano particle of 10 nanometers by diameter; If the addition of sulphur too much, the mol ratio of Zn and S is less than 1:1, then have to zincblende ZnS nano particle.
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| CN103382576B (en) * | 2012-05-04 | 2015-10-14 | 北京化工大学 | Cubic crystal zinc sulfide material of a kind of cupric sulfide doping and preparation method thereof |
| CN105742389B (en) * | 2016-04-13 | 2017-05-10 | 电子科技大学 | Synthesis method of copper-indium-gallium-sulphur material, thin-film solar cell and preparation method of thin-film solar cell |
| CN112779012A (en) * | 2019-11-11 | 2021-05-11 | 欣盛光电股份有限公司 | Core-shell luminescent quantum dot material and manufacturing method thereof |
| CN114835155B (en) * | 2022-04-22 | 2022-12-09 | 哈尔滨理工大学 | Preparation method of ZnS nano material |
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| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
| CN101077976A (en) * | 2007-06-28 | 2007-11-28 | 复旦大学 | Method of preparing CdTe/CdS/ZnS core-shell-core structure quantum points |
| CN101121517A (en) * | 2007-07-09 | 2008-02-13 | 燕山大学 | Conductive superhard material BxCy compound and preparation method thereof |
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| JP2004182810A (en) * | 2002-12-02 | 2004-07-02 | Mitsui Mining & Smelting Co Ltd | Thin-film electroluminescence material and manufacturing method therefor |
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| CN101077976A (en) * | 2007-06-28 | 2007-11-28 | 复旦大学 | Method of preparing CdTe/CdS/ZnS core-shell-core structure quantum points |
| CN101121517A (en) * | 2007-07-09 | 2008-02-13 | 燕山大学 | Conductive superhard material BxCy compound and preparation method thereof |
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