CN1226192C - Process for preparing hollow ball of single dispersion cadmium sulfide - Google Patents
Process for preparing hollow ball of single dispersion cadmium sulfide Download PDFInfo
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- CN1226192C CN1226192C CN 200410016496 CN200410016496A CN1226192C CN 1226192 C CN1226192 C CN 1226192C CN 200410016496 CN200410016496 CN 200410016496 CN 200410016496 A CN200410016496 A CN 200410016496A CN 1226192 C CN1226192 C CN 1226192C
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- Prior art keywords
- ball
- cadmium sulfide
- monodisperse
- hollow ball
- cadmium
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- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 34
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000006185 dispersion Substances 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 4
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000004038 photonic crystal Substances 0.000 abstract description 3
- 238000000224 chemical solution deposition Methods 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000011022 opal Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 239000004991 Lytropic liquid crystal Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention discloses a method for preparing a monodisperse cadmium sulfide hollow ball, which adopts a chemical bath deposition method and comprises the following steps: firstly, dispersing a monodisperse SiO2 ball with uniform particle diameter in a deionized water solution with ultrasonic vibration, adding trisodium citrate dihydrate as a complexing agent, adopting ammonia water to adjust the pH value to 8 to 13, magnetically stirring the mixture at constant temperature of 50 to 90 DEG C, and adding cadmium chloride and thiourea for reaction for 1 to 2 hours to prepare core-shell structure in which the SiO2 ball is coated by cadmium sulfide; secondly, corroding the core of the SiO2 with diluted hydrofluoric acid to prepare a cadmium sulfide hollow ball; finally, circularly washing the cadmium sulfide hollow ball by deionized water and absolute alcohol with centrifugal deposition and ultrasonic dispersion to remove the residual reactants, and drying the washed ball to prepare a monodisperse cadmium sulfide hollow ball. The simple and practicable method of the present invention can prepare monodisperse cadmium sulfide hollow balls which are used as structural primitives to prepare three-dimensional photonic crystal with high refractive index contrast, a large duty cycle and a complete photonic band gap.
Description
Technical field
The present invention relates to prepare the method for monodisperse CdS hollow ball.
Background technology
Photonic crystal is the artificial microstructure that can be compared with optical wavelength by its cycle that the material with differing dielectric constant (specific refractory power) is arranged according to certain spacial ordering.As " optical semiconductor ", photonic crystal has the function of unique adjusting light spread state, and, fields such as photon integrated, optical communication integrated at photoelectricity have boundless application prospect.In recent years, the research of three-D photon crystal has caused more and more investigators' interest, and preparation three-D photon crystal method commonly used is that monodispersity balls such as silica spheres or polystyrene are self-assembled into the opal structural with center of area solid matter under the certain force field action.But this preparation method is difficult to prepare large-area ordered structure, and this structure of preparing simultaneously can not satisfy the requirement (being dutycycle＞80% and index contrast＞2.8) that preparation has the photon crystal material of complete band gap; Also need in opal, to fill again high-index material, and then silicon-dioxide or polystyrene are removed with the method for preferential etch, obtain counter opal structure.
Has high refractive index hollow ball material (as Cadmium Sulfide) has center of area solid matter from composition as structural unit opal structural and utilize, can satisfy the requirement that preparation has the three-D photon crystal of complete photonic band gap, strengthen the photon band gap characteristic of this structure greatly.
Cadmium Sulfide (CdS) is that a kind of very important IV-VI family has direct wide bandgap semiconductor materials, is widely used in electronics, optoelectronic areas.Because this material has high relatively specific refractory power and superior optical property, also is widely used in the photonic material field in recent years.The preparation of hollow cadmium sulphide ball has several different methods, for example adopts lytropic liquid crystals, dithiocarbonic anhydride drop, polystyrene acid particles, both sexes three multipolymers etc. to be template, at first prepares nucleocapsid structure, template is removed obtained cadmium sufide hollow ball then.When the preparation nucleocapsid structure, need to carry out pre-treatment to examining the surface earlier, and because the template that adopts is not a monodispersity, the cadmium sufide hollow ball of these method preparations does not have monodispersity, and the thickness of ball wall is uncontrollable.
Summary of the invention
The objective of the invention is for obtaining to have the three-D photon crystal of complete photonic band gap, the method for the monodisperse CdS hollow ball that a kind of preparation has high refractive index is provided.
The method for preparing the monodisperse CdS hollow ball of the present invention, employing be chemical bath deposition, may further comprise the steps:
1) the uniform monodisperse silica sphere particle of particle diameter is dispersed in the deionized water solution with sonic oscillation, add Trisodium Citrate and make complexing agent, and regulate pH value to 8～13 with ammoniacal liquor, 50 ℃～90 ℃ constant temperature magnetic agitation, add Cadmium chloride fine powder and thiocarbamide then, the concentration that makes Cadmium chloride fine powder in the solution is 0.001 mol～0.01 mol, and the concentration of thiocarbamide is 0.002 mol～0.02 mol, reacted 1～2 hour, and obtained the nucleocapsid structure of Cadmium Sulfide parcel silica spheres;
2) with the dilute hydrofluoric acid corrode silicon dioxide core of 1%-10%, obtain hollow cadmium sulphide ball;
3) adopt centrifugal deposition to add the ultra-sonic dispersion wash cycles with deionized water and dehydrated alcohol, remove reaction residue, oven dry obtains the monodisperse CdS hollow ball.
The hydrofluoric acid concentration that dilutes among the present invention is generally 1%～10%.Monodisperse silica sphere particle can be commercially available or by " Si Tuobu (Stober) method " preparation, particle diameter is that 10nm is to 1000nm.
The inventive method can be regulated the sphere diameter of hollow ball by changing the particle diameter of silicon-dioxide ball template; Change the concentration of Cadmium chloride fine powder and thiocarbamide, can regulate the wall thickness of hollow ball.
Method of the present invention is template with the monodisperse silica sphere particle, and silica spheres is compared with polystyrene spheres and can high temperature heat-resistant be handled.By the deposition of chemical bath in alkaline aqueous solution, need not carry out pre-treatment to the silica spheres surface again, just can obtain nucleocapsid structure, method is simple.Chemical corrosion silica core then obtains the monodisperse CdS hollow ball of uniform particle diameter.The monodisperse CdS hollow ball that the present invention makes can be used as structural motif, and preparation has high-index contrast and the big three-D photon crystal of dutycycle, obtains having the three-D photon crystal of complete photonic band gap.Utilization has the hollow cadmium sulphide ball of high refractive index has center of area solid matter from composition as structural unit opal structural, the preparation method is simple, not only can satisfy the requirement that preparation has the three-D photon crystal of complete photonic band gap, strengthen the photon band gap characteristic of this structure greatly, can also regulate the residing position of photon band gap by the sphere diameter and the wall thickness that change hollow ball.
Description of drawings
Fig. 1 is a Cadmium Sulfide nucleocapsid structure transmission electron microscope photo, and wherein: figure a) for the transmission electron microscope photo of Cadmium Sulfide parcel silica spheres nucleocapsid structure, schemes b) be the transmission electron microscope photo of monodisperse hollow cadmium sulphide ball;
Fig. 2 is the transmission electron microscope photo of single cadmium sufide hollow ball, and the upper left corner is its electron diffraction;
Fig. 3 is the field emission scanning electron microscope photo of cadmium sufide hollow ball;
Fig. 4 is the XRD figure spectrum of hollow cadmium sulphide ball.
Embodiment
Embodiment:
1) monodisperse silica sphere particle that is 430nm with 300 milligrams of particle diameters is dispersed in the 250 ml deionized water solution with sonic oscillation, and the Trisodium Citrate that adds 10 milliliter of 0.1 mol is made complexing agent, and regulates pH value to 11 with ammoniacal liquor.60 ℃ of constant temperature magnetic agitation, drip the Cadmium chloride fine powder of 10 milliliter of 0.1 mol and the thiocarbamide of 50 milliliter of 0.04 mol then, reacted 2 hours, the nucleocapsid structure that obtains Cadmium Sulfide parcel silica spheres is (as Fig. 1 a);
2) with 1 to 10 dilute hydrofluoric acid erosion removal silica core, obtain hollow cadmium sulphide ball;
3) adopt centrifugal deposition to add the ultra-sonic dispersion wash cycles with deionized water and dehydrated alcohol, remove reaction residue, 60 ℃ of oven dry obtain monodisperse CdS hollow ball (as Fig. 1 b).
Fig. 2 is the transmission electron microscope photo of the single cadmium sufide hollow ball that makes, has provided the electron diffraction spot simultaneously among the figure, and visible cadmium sulphide ball is a polycrystalline.
Fig. 3 is a use emission scan electron microscopic observation cadmium sufide hollow ball, has hollow structure really from visible its of wherein broken sample.
Products therefrom is XRD tests its crystalline structure, as shown in Figure 4, the component of visible resulting hollow ball is the Cadmium Sulfide with hexaplanar structure really.
Claims (1)
1. the method for preparing the monodisperse CdS hollow ball is characterized in that may further comprise the steps:
1) the uniform monodisperse silica sphere particle of particle diameter is dispersed in the deionized water solution with sonic oscillation, add Trisodium Citrate and make complexing agent, and regulate pH value to 8～13 with ammoniacal liquor, 50 ℃～90 ℃ constant temperature magnetic agitation, add Cadmium chloride fine powder and thiocarbamide then, the concentration that makes Cadmium chloride fine powder in the solution is 0.001 mol～0.01 mol, and the concentration of thiocarbamide is 0.002 mol～0.02 mol, reacted 1～2 hour, and obtained the nucleocapsid structure of Cadmium Sulfide parcel silica spheres;
2) be the dilute hydrofluoric acid corrode silicon dioxide core of 1%-10% with concentration, obtain hollow cadmium sulphide ball;
3) adopt centrifugal deposition to add the ultra-sonic dispersion wash cycles with deionized water and dehydrated alcohol, remove reaction residue, oven dry obtains the monodisperse CdS hollow ball.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410016496 CN1226192C (en) | 2004-02-20 | 2004-02-20 | Process for preparing hollow ball of single dispersion cadmium sulfide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410016496 CN1226192C (en) | 2004-02-20 | 2004-02-20 | Process for preparing hollow ball of single dispersion cadmium sulfide |
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| CN1559911A CN1559911A (en) | 2005-01-05 |
| CN1226192C true CN1226192C (en) | 2005-11-09 |
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| CN 200410016496 Expired - Fee Related CN1226192C (en) | 2004-02-20 | 2004-02-20 | Process for preparing hollow ball of single dispersion cadmium sulfide |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331757C (en) * | 2005-11-23 | 2007-08-15 | 南京师范大学 | Process for preparing nano-grade cadmium sufide hollow ball |
| CN101058437B (en) * | 2007-04-10 | 2010-10-06 | 安徽大学 | Liquid state preparation method for nano cadmium sulfide hollow sphere |
| CN101319404B (en) * | 2008-06-10 | 2012-05-16 | 浙江大学 | Method for preparation of hollow spherical cadmium sulfide nanocrystalline |
| CN101870588B (en) | 2009-04-21 | 2012-10-31 | 河北勇龙邦大新材料有限公司 | Method and device for preparing hollow ceramic microspheres |
| CN104722775B (en) * | 2015-03-11 | 2016-09-07 | 浙江大学 | A kind of two dimension hollow palladium nano-crystal and preparation method thereof |
| CN106513018B (en) * | 2016-09-30 | 2019-08-02 | 江苏大学 | A kind of core-shell structure ZnFe2O4The preparation method and its usage of@CdS composite photo-catalyst |
| WO2019130058A2 (en) * | 2017-12-28 | 2019-07-04 | D. Swarovski Kg | Method and apparatus for manufacturing photonic crystals |
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- 2004-02-20 CN CN 200410016496 patent/CN1226192C/en not_active Expired - Fee Related
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| CN1559911A (en) | 2005-01-05 |
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