CN103771494A - Liquid-phase preparation method for manganese-doped zinc sulfide microspheres - Google Patents
Liquid-phase preparation method for manganese-doped zinc sulfide microspheres Download PDFInfo
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- CN103771494A CN103771494A CN201410037398.6A CN201410037398A CN103771494A CN 103771494 A CN103771494 A CN 103771494A CN 201410037398 A CN201410037398 A CN 201410037398A CN 103771494 A CN103771494 A CN 103771494A
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Abstract
The invention belongs to the technical field of semiconductor nano material preparation and in particular relates to a liquid-phase preparation method for manganese-doped zinc sulfide microspheres. The preparation method comprises the steps of preparing a solvent A through 2-hydroxy ethylamine and water, weighing and putting a zinc source, a manganese source and a sulfur source into the solvent A, stirring to dissolve the sources to prepare a solution B, and adding a structural inductive agent into the solution B to form a solution C; transferring the solution C into a reaction kettle with a Teflon inner container, closing the reaction kettle, putting the reaction kettle into a drying oven for heating, performing natural cooling to room temperature, separating products, cleaning the products with distilled water and ethyl alcohol, drying and collecting the products which are the manganese-doped zinc sulfide microspheres. According to the preparation method, the 2-hydroxy ethylamine and the water are used as the solvents, and ethanediamine is used as the structural inductive agent; by adjusting the adding amount of the ethanediamine, the target manganese-doped zinc sulfide product is synthesized in the reaction kettle by one step; doping is easy, operation is simple, the cost is low, and industrialization is facilitated.
Description
Technical field
The invention belongs to semiconductor nano material preparing technical field, be specifically related to a kind of liquid phase preparation process of manganese doped zinc sulphide microballoon.
Background technology
Semiconductor nano material becomes one of study hotspot of current Material Field with its unique physics and chemistry character.ZnS, as the typical 11-VI of one family semiconductor material, there is the features such as band gap length, good conductivity, be widely used in the aspects such as flat-panel monitor, infrared detector, photo luminescent devices, infrared window, solar cell, sensor, laser apparatus and photochemical catalysis.In addition, people find on the basis of lot of experiments, ZnS are carried out to dopant activation with suitable element, can make ZnS semiconductor material have and its diverse optical property when microstate or the macroscopical thing piece, have huge application potential.Particularly rare earth metal or transition metal element doped ZnS crystallo-luminescence material, is expected to playing a significant role aspect manufacture electronics or photoelectron nano-device.Wherein, manganese doped zinc sulphide is as a kind of orange luminescence material, and luminous efficiency is high, chemical stability is strong, can, for practical application area such as negative ray, X ray and luminescence sensors, be subject to people's broad research and attention.
People have adopted pulsed laser deposition at present, thermal evaporation, molecular beam epitaxy, microemulsion, collosol and gel, chemical vapour deposition, numerous physical methods such as template and chemical process are prepared Mn doped ZnS nano particle (Nag A, Chakraborty S, Sarma D D.J.Am.Chem.Soc.2008, 130, 10605-10611.), nanometer rod (Biswas S, Kar S, Chaudhuri S.J.Phys.Chem.B2005, 109, 17526-17530.), nano wire (Brieler F J, Grundmann P, Froba M, et al.J.Am.Chem.Soc.2004, 126, 797-807.), nano belt (Geng B Y, Zhang L D, Wang G Z, et al.Appl.Phys.Lett.2004, 84, 2157-2159.) etc., the Mn doped ZnS nanostructure material product that the people such as Chang Yongqin adopt chemical Vapor deposition process to prepare to be made up of nano wire and nano belt in patent CN101254940A.Although prepared the Mn doped ZnS of different-shape by said synthesis route nanocrystalline, the synthetic Mn doped ZnS microballoon with thorn-like also rarely has report.In addition the nanocrystalline synthetic method of most of Mn doped ZnSs, needs harsh reaction conditions, the difficult doping of mn ion, and product is wayward, is unfavorable for low-coat scaleization production.Therefore, design a kind of cost low, the synthetic method of the ZnS microballoon of the easy controlled doping of mn ion, remains the challenge that we face.
Summary of the invention
The liquid phase preparation process that the object of this invention is to provide a kind of manganese doped zinc sulphide microballoon, mn ion easily adulterates, reaction temperature and, raw material is cheap and easy to get, product is easily controlled.
The liquid phase preparation process of manganese doped zinc sulphide microballoon of the present invention, step is as follows:
(1) measure 2 hydroxy ethylamine and water is configured to solvent orange 2 A, then take zinc source, solvent orange 2 A is put in He Liu source, manganese source, stirring and dissolving forms solution B, adds subsequently structure inducer to form solution C in solution B;
(2) solution C is transferred in the reactor of Teflon inner bag, airtight being placed in baking oven heated, and naturally cools to room temperature, by product separation, cleans successively with distilled water and ethanol, and after being dried, collection product obtains manganese doped zinc sulphide microballoon.
The volume ratio of the 2 hydroxy ethylamine described in step (1) and water is 1:2-12:1.
Zinc source described in step (1) is the one in zinc acetate, zinc nitrate or zinc sulfate, and manganese source is the one in manganous acetate, manganous nitrate or manganous sulfate, and sulphur source is thiocarbamide.
Described in step (1), the concentration of zinc source in solution C is 0.0125-0.1mol/L.
The mol ratio in the He Liu source, zinc source described in step (1) is 1:1.5-1:3.
In manganese source described in step (1), the doping quality of Mn is the 0.1-10at.% of He Meng source, zinc source total mass.
Structure inducer described in step (1) is quadrol, and the volume ratio of structure inducer and 2 hydroxy ethylamine is 1:1-1:36.
Churning time described in step (1) is 2-8 minute.
Heating temperature described in step (2) is 150-200 ℃, and be 12-30h heat-up time.
Distilled water wash number described in step (2) is 2-6 time, and ethanol wash number is 2-6 time.
Drying temperature described in step (2) is 40-80 ℃, and be 4-12h time of drying.
The liquid phase preparation process of manganese doped zinc sulphide microballoon of the present invention, preferred steps is as follows:
(1) measure 2 hydroxy ethylamine and water and be mixed with the solvent orange 2 A that volume ratio is 1:2-12:1, take zinc acetate and thiocarbamide, wherein the mol ratio of zinc acetate and thiocarbamide is 1:1.5-1:3, the 0.1-10at.% that is He Meng source, zinc source total mass by manganese doping quality takes manganous acetate, these three kinds of reactants are added to solvent orange 2 A, stir and within 2-8 minute, dissolve formation solution B, measure quadrol and add solution B, formation solution C stirs;
(2) solution C is transferred in Teflon reactor, airtight being placed in baking oven heated 15-30h under 150-200 ℃ of condition, then naturally cools to room temperature; The cooling good product of reaction is taken out to centrifugation from reactor, first use distilled water wash 2-6 time, then use absolute ethanol washing 2-6 time, finally put into loft drier, under 40-80 ℃ of condition, dry 4-12h, obtains manganese doped zinc sulphide microballoon.
Fig. 1 is that Mn doping is the photoluminescence spectrogram of 0.5%, 1%, 2%, 3%, 5%, 8% ZnS microballoon.As shown in Figure 1, the doping of manganese is adjustable, and in the time that the doping of manganese is 3%, product has the strongest orange luminescence, and mn ion is the main light-emitting element of manganese doped zinc sulphide acanthosphere.
The present invention compared with prior art, has following beneficial effect:
2 hydroxy ethylamine and water as solvent for the present invention, quadrol does structure inducer, by regulating the add-on of quadrol, one-step synthesis manganese doped zinc sulphide target product in reactor, adulterate easy, simple to operate, cost is low, be easy to industrialization.
Accompanying drawing explanation
Fig. 1 is that Mn doping is the photoluminescence spectrogram of 0.5%, 1%, 2%, 3%, 5%, 8% ZnS microballoon.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 1 product.
Fig. 3 is the X-ray diffractogram of embodiment 1 product.
Fig. 4 is that the EDS of embodiment 1 product can spectrogram.
Fig. 5 is the scanning electron microscope (SEM) photograph of embodiment 4 products.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
(1) 2 hydroxy ethylamine, the 20ml water that measure 10ml are mixed with the solvent orange 2 A that volume ratio is 1:2, by 0.5mmol zinc acetate, 0.005mmol manganous nitrate (doping is 1%), 0.75mmol thiocarbamide joins solvent orange 2 A, the mol ratio of zinc acetate and thiocarbamide is 1:1.5, stir and form solution B in 2 minutes, in solution B, add subsequently the 10ml quadrol formation solution C that stirs;
(2) solution C is transferred in Teflon reactor, airtight being placed in baking oven heated 12h under 200 ℃ of conditions, then naturally cools to room temperature, first uses distilled water wash 3 times, then uses absolute ethanol washing 3 times, and 80 ℃ of dry 4h, obtain product.
As shown in Figure 2, product is that the acanthosphere being formed by nanometer rod self-assembly forms, diameter 2 μ m.As shown in Figure 3, XRD test shows that product has hexagonal structure, without the appearance of MnS and other impurity peaks, proves Mn
2+be doped in ZnS lattice.As shown in Figure 4, EDS test shows that product major ingredient is Zn, Mn and tri-kinds of elements of S, can find out that from Fig. 1 b photoluminescence spectrogram Mn doped ZnS has an orange luminescence peak at 580nm, further shows Mn
2+be doped to ZnS intracell.
(1) 2 hydroxy ethylamine, the 15ml water that measure 15ml are mixed with the solvent orange 2 A that volume ratio is 1:1, by 4mmol zinc acetate, 0.131mmol manganous acetate (doping is 3%), 8mmol thiocarbamide joins solvent orange 2 A, the mol ratio of zinc acetate and thiocarbamide is 1:2, stir and form solution B in 8 minutes, in solution B, add subsequently the 10ml quadrol formation solution C that stirs;
(2) solution C is transferred in Teflon reactor, airtight being placed in baking oven heated 20h under 180 ℃ of conditions, then naturally cool to room temperature, first use distilled water wash 2 times, then use absolute ethanol washing 6 times, 60 ℃ of dry 6h, obtain manganese doped zinc sulphide acanthosphere, acanthosphere diameter 1.5 μ m.From Fig. 1 d, ZnS has a very strong orange luminescence at 580nm place, show Mn
2+be doped to ZnS intracell.The X-ray diffractogram of product is identical with embodiment 1.
(1) 2 hydroxy ethylamine, the 8ml water that measure 24ml are mixed with the solvent orange 2 A that volume ratio is 3:1, by 1mmol zinc acetate, 0.031mmol manganous sulfate (doping is 5%), 3mmol thiocarbamide joins solvent orange 2 A, the mol ratio of zinc acetate and thiocarbamide is 1:3, stir and form solution B in 5 minutes, in solution B, add subsequently 8ml quadrol to stir and form solution C.
(2) solution C is transferred in Teflon reactor, airtight being placed in baking oven, under 150 ℃ of conditions, heat 30h, then naturally cool to room temperature, first use distilled water wash 6 times, then use absolute ethanol washing 2 times, 40 ℃ of vacuum-drying 12h, obtain manganese doped zinc sulphide acanthosphere, acanthosphere diameter 2.5 μ m.From Fig. 1 e, ZnS has an orange luminescence at 580nm place, shows Mn
2+be doped to ZnS intracell.The X-ray diffractogram of product is identical with embodiment 1.
2 hydroxy ethylamine in embodiment 2 is become to 32ml, and water becomes 4ml, and volume ratio becomes 8:1, and quadrol becomes 4ml, and churning time becomes 8 minutes, and other reaction process and condition are constant.
As shown in Figure 5, product is the acanthosphere that is formed diameter 1 μ m by nanometer rod self-assembly.The photoluminescence spectrogram of product is with embodiment 2, and the X-ray diffractogram of product is identical with embodiment 1.
2 hydroxy ethylamine in embodiment 2 is become to 36ml, and water becomes 3ml, and volume ratio becomes 12:1, and quadrol becomes 1ml, and churning time becomes 8 minutes, and other reaction process and condition are constant.
Product is the acanthosphere of diameter 3 μ m, and photoluminescence spectrogram is with embodiment 2, and X-ray diffractogram is identical with embodiment 1.
By the manganous acetate doping (3%) in embodiment 2, with 0.5% substitute, other reaction process and condition are constant, luminous Fig. 1 a that the results are shown in of product, X-ray diffractogram is identical with embodiment 1.
By the manganous acetate doping (3%) in embodiment 2, substitute with 2%, other reaction process and condition are constant, luminous Fig. 1 c that the results are shown in of product, X-ray diffractogram is identical with embodiment 1.
By the manganous acetate doping (3%) in embodiment 2, substitute with 8%, other reaction process and condition are constant, luminous Fig. 1 f that the results are shown in of product, X-ray diffractogram is identical with embodiment 1.
Zinc acetate in embodiment 2 is substituted with zinc nitrate, and other reaction process and condition are constant, and pattern, the crystalline phase of products therefrom are identical with embodiment 1, and photoluminescence spectrogram is with embodiment 2.
Zinc acetate in embodiment 2 is substituted with zinc sulfate, and other reaction process and condition are constant, and pattern, the crystalline phase of products therefrom are identical with embodiment 1, and photoluminescence spectrogram is with embodiment 2.
Claims (10)
1. a liquid phase preparation process for manganese doped zinc sulphide microballoon, is characterized in that step is as follows:
(1) measure 2 hydroxy ethylamine and water is configured to solvent orange 2 A, then take zinc source, solvent orange 2 A is put in He Liu source, manganese source, stirring and dissolving forms solution B, adds subsequently structure inducer to form solution C in solution B;
(2) solution C is transferred in the reactor of Teflon inner bag, airtight being placed in baking oven heated, and naturally cools to room temperature, by product separation, cleans successively with distilled water and ethanol, and after being dried, collection product obtains manganese doped zinc sulphide microballoon.
2. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, the volume ratio that it is characterized in that the 2 hydroxy ethylamine described in step (1) and water is 1:2-12:1.
3. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, it is characterized in that the zinc source described in step (1) is the one in zinc acetate, zinc nitrate or zinc sulfate, manganese source is the one in manganous acetate, manganous nitrate or manganous sulfate, and sulphur source is thiocarbamide.
4. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, is characterized in that described in step (1), the concentration of zinc source in solution C is 0.0125-0.1mol/L.
5. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, is characterized in that the mol ratio in the He Liu source, zinc source described in step (1) is 1:1.5-1:3.
6. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, the doping quality that it is characterized in that Mn in the manganese source described in step (1) is the 0.1-10at.% of He Meng source, zinc source total mass.
7. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, is characterized in that the structure inducer described in step (1) is quadrol, and the volume ratio of structure inducer and 2 hydroxy ethylamine is 1:1-1:36.
8. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, is characterized in that the Heating temperature described in step (2) is 150-200 ℃, and be 12-30h heat-up time.
9. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, is characterized in that the distilled water wash number described in step (2) is 2-6 time, and ethanol wash number is 2-6 time.
10. the liquid phase preparation process of manganese doped zinc sulphide microballoon according to claim 1, is characterized in that the drying temperature described in step (2) is 40-80 ℃, and be 4-12h time of drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114114472A (en) * | 2021-12-01 | 2022-03-01 | 上海应用技术大学 | Method for preparing photonic crystal by manganese ion doped zinc sulfide microsphere self-assembly |
| CN114602508A (en) * | 2022-04-02 | 2022-06-10 | 吉林化工学院 | Preparation and application of MnS @ ZnS core-shell hollow sphere with photocatalytic performance |
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| CN102097206A (en) * | 2009-12-09 | 2011-06-15 | 吉林师范大学 | Low temperature growth method for wurtzite zinc sulfide base diluted magnetic semiconductor nanorod |
| CN102249289A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing spiauterite ZnS fine nanorod with solvothermal method |
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2014
- 2014-01-26 CN CN201410037398.6A patent/CN103771494A/en active Pending
Patent Citations (2)
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| CN102097206A (en) * | 2009-12-09 | 2011-06-15 | 吉林师范大学 | Low temperature growth method for wurtzite zinc sulfide base diluted magnetic semiconductor nanorod |
| CN102249289A (en) * | 2011-05-27 | 2011-11-23 | 新疆大学 | Method for preparing spiauterite ZnS fine nanorod with solvothermal method |
Non-Patent Citations (2)
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| 王新娟: ""几种半导体纳米材料的液相控制合成、形成机理及性能研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114114472A (en) * | 2021-12-01 | 2022-03-01 | 上海应用技术大学 | Method for preparing photonic crystal by manganese ion doped zinc sulfide microsphere self-assembly |
| CN114602508A (en) * | 2022-04-02 | 2022-06-10 | 吉林化工学院 | Preparation and application of MnS @ ZnS core-shell hollow sphere with photocatalytic performance |
| CN114602508B (en) * | 2022-04-02 | 2023-08-04 | 吉林化工学院 | Preparation and application of MnS@ZnS core-shell hollow sphere catalyst with photocatalytic performance |
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Application publication date: 20140507 |