CN1289180C - Method for preparing two-dimensional or three dimensional colloid crystal - Google Patents
Method for preparing two-dimensional or three dimensional colloid crystal Download PDFInfo
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- CN1289180C CN1289180C CN200410041939.9A CN200410041939A CN1289180C CN 1289180 C CN1289180 C CN 1289180C CN 200410041939 A CN200410041939 A CN 200410041939A CN 1289180 C CN1289180 C CN 1289180C
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- microcavity
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- 239000013078 crystal Substances 0.000 title claims abstract description 53
- 239000000084 colloidal system Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 239000004005 microsphere Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 230000005484 gravity Effects 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000011806 microball Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 3
- 230000008520 organization Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 12
- 238000000151 deposition Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 239000010453 quartz Substances 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011805 ball Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
The present invention relates to a method for preparing two-dimensional colloid crystal and three-dimensional colloid crystal. A microcavity system is arranged in a space be spaced by two flat plates in parallel, wherein three surfaces of the microcavity system are sealed, and one end of the microcavity system is opened; liquid colloidal suspension is firstly injected into the microcavity, and then the microcavity system is opened towards the inclined lower part. Because the gravity of a microsphere is more than the buoyancy of the suspension to the microsphere, the microsphere firstly forms an unordered close-packed structure on a substrate of the microcavity, and then the microsphere carries out self organization to form an ordered structure under the secondary function of the surface tension of the microsphere in the drying process of the liquid colloidal suspension in the microcavity from the opening of the microcavity to the inside of the microcavity, namely in the continuous moving process of a liquid surface from the opening position of the microcavity to the inside of the microcavity. The present invention has the advantages of simple technical process, short preparing period and high efficiency and can prepare two-dimensional colloidal crystal and three-dimensional colloidal crystal with large area, high quality and long-range ordered structure.
Description
One, technical field
The present invention relates to a kind of preparation of colloidal crystal material, particularly, the colloid micro ball (particularly at the silicon dioxide microsphere of diameter greater than 1 micron) of big quality is arranged in the method for individual layer (two dimension) and face-centred cubic multilayer (three-dimensional) the structure colloidal crystal of hexagonal Mi Dui by the capillary double action of self assembly under the gravity effect and liquid.
Two, background technology
The research of the two and three dimensions colloidal crystal that, the micron monodispersed to utilizing or the colloid micro ball of sub-micron are formed not only has important scientific research value, and has important practical value.For example, can be used as the template for preparing high-sequential porous material, prepare high-intensity pottery as precursor.In addition, because colloidal crystal has special optical diffraction characteristic and exists photon band gap, make this class material can be used to prepare optical filter, optical switch, chemistry and biology sensor and optics integrated chip etc.
By the research of more than ten years, people have been developed several different methods makes colloid micro ball form orderly colloidal crystal.The self assembling process that these technologies of preparing are often taken place under the effect of some certain force by means of colloid micro ball.Summary is got up, and these methods can be divided into deposition under driving of deposition under the weight-driven, electrostatic force, extra electric field induction and deposition, compression molding techniques, vertical deposition, pattern growth technology or the like.
Figure 1A has shown pure deposition schematic diagram under the gravitational field effect, referring to K.E.Davis, and W.B.Russel, W.J.Glantschnig, Sicence 1989,245, and 507.Often contain the more point or the polycrystalline of planar defect in the colloidal crystal that adopts this method to obtain, and the thickness of crystal is also restive, the manufacturing cycle of this method is not only longer, also is not suitable for the colloid micro ball of those self gravitations greater than the buoyancy in suspension.
The method that adopts self-organizing under the electrostatic repulsion forces to obtain colloidal crystal is to rely on the electrostatic repulsion forces between the charged microballoon and form orderly structure, referring to N.Ise, and Angew.Chem.Int.Ed.Engl.1986,25,323.This method except require microballoon charged, also want the concentration of colloid in the strict control suspension, otherwise obtain be likely that body-centered cubic phase, face-centered cubic are mutually or unordered phase.The same with the gravity sedimentation method, this method is to the disturbance sensitivity.
The extra electric field induction and deposition requires the surface of colloid micro ball with the electric charge of going up a great deal of, simultaneously the requirement of strength of electric field is accurately controlled.
Figure 1B is the schematic diagram of compression molding techniques, referring to Y.Xia, and B.Gates, Y.Yin, Y.Lu, Adv.Mater.2002,12693.The advantage of this technology is to be applied to neutral ball; Can obtain colloidal crystal large-area, controllable thickness; To the size of microballoon in principle without limits.But for the especially little microballoon of size, because its pressing mold involves photoetching technique, the corresponding increase of difficulty; And for greater than 1 micron silicon dioxide microsphere, because its quality is too big, the driving force of liquid stream is not enough to make microballoon to continue to form ordered structure in the ordered structure near interface self-organizing that has formed.
Fig. 1 C has shown the schematic diagram of vertical deposition method, referring to J.D.Joannopoulos, and Nature, 2001,414,257.Compare with the technology of front, this method is easily prepared large tracts of land, high-quality single domain colloidal crystal.For the colloid micro ball of those self gravitations greater than its buoyancy in suspension, this technology is inapplicable equally.This is because of the very fast sinking of these microballoons under these circumstances, and can not deposit on substrate.
We are once with regard to the colloidal crystal technology of preparing, applied for a national inventing patent, patent name is: " colloid micro ball self-organizing under the capillary attraction and two dimension, three-dimensional colloidal crystal preparation method ", this number of patent application is 03131989.0, publication number is CN1470319A.What this patent related generally to is by capillary force, the suspension of monodisperse polystyrene colloid microballoon is spontaneously sucked in the microchannel, and the self assembling process by being taken place in the microchannel, prepares the method for two and three dimensions colloidal crystal.This technology is applicable to the polystyrene microsphere or the less silicon dioxide microsphere of diameter of lightweight, but also is not suitable for the silicon dioxide microsphere of diameter in the big quality more than 1 micron.Reason is: for heavier microballoon, though capillary force can constantly be urged to solvent in the microchannel, form ground liquid stream in the microchannel and can't the microballoon that these are heavier bring to the port of passage and self-organizing.
Three, summary of the invention
The present invention seeks to: under weight-driven,, on a substrate that finally makes microballoon at microcavity under the capillary secondary action, form in order and arrange microballoon assembling in advance in microcavity.
The method that the present invention adopts is: in the space of one two dull and stereotyped parallel interval, be provided with the microcavity system of one three sealings, an end opening, earlier the colloid suspension injected in the microcavity.Microcavity system opening is to oblique below then, because the gravity of microballoon is greater than the buoyancy of suspension to it, microballoon at first forms a unordered solid matter structure on a substrate of microcavity, utilize then colloid suspension in the microcavity from opening to the dry run of inside, be liquid level from the process that the aperture position of microcavity constantly moves inward, microballoon self-organizing and form ordered structure under its capillary secondary action.
Among the present invention, the gradient of microcavity is controlled in 5 °.
Among the present invention, control the thickness of the colloidal crystal that forms by the concentration of control microballoon emulsion.
Among the present invention, given composition colloidal crystal number of plies N
1, sept thickness D, microsphere diameter d, the turbid liquid volume concentrations of colloidal suspension C
vMust satisfy:
The present invention is applicable to the self assembling process of gravity greater than the colloid micro ball of colloid suspension buoyancy, has particularly solved the technical problem of diameter greater than the silicon dioxide microsphere self-organizing assembling of 1 micron big quality.
The volume that the present invention can also be by regulating microcavity and the concentration of colloid suspension are controlled the thickness of colloidal crystal.Thicker colloidal crystal needs the concentration height of the big and colloid suspension of the volume of microcavity.
Characteristics of the present invention are: technical matters is simple, and manufacturing cycle is short, and the efficient height can be prepared the colloidal crystal of large-area, high-quality two and three dimensions long range ordered structure.
Four, description of drawings
Below in conjunction with accompanying drawing, and the invention will be further described to pass through example:
Figure 1A has shown pure deposition schematic diagram under the gravitational field effect; Figure 1B is the schematic diagram of compression molding techniques; Fig. 1 C has shown the schematic diagram of vertical deposition method.Fig. 1 D has shown the colloid micro ball method schematic diagram under the capillary attraction in the microchannel.About the detailed content of these technology, see relevant document.
Fig. 2 is a constructional device schematic diagram of the present invention.
Fig. 3 adopts regional area SEM (SEM) photo of the two-dimensional colloidal crystal that the monodisperse silica microspheres of 1 micron of diameter makes for the present invention.
Fig. 4 adopts the SEM photo on the three-dimensional colloidal crystal surface that the monodisperse silica microspheres of 1 micron of diameter makes for the present invention.
Fig. 5 adopts the partial zones SEM photo of individual layer (two dimension) colloidal crystal that the monodisperse silica microspheres of 1.6 microns of diameters makes for the present invention.
Multilayer (accurate three-dimensional) the colloidal crystal surface topography SEM photo that Fig. 6 adopts the monodisperse silica microspheres of 1.6 microns of diameters to make for the present invention.
Fig. 7 adopts the fringe region SEM photo of the three-dimensional colloidal crystal that the monodisperse silica microspheres of 1.6 microns of diameters makes for the present invention.
Fig. 8 adopts the partial zones SEM photo of the two-dimensional colloidal crystal that the monodisperse silica microspheres of 5 microns of diameters makes for the present invention.
Five, the specific embodiment
The present invention is by the self assembling process of colloid micro ball in microcavity under gravity and capillary acting in conjunction, prepares high-quality two and three dimensions colloidal crystal.Implementation method is seen Fig. 2.
The present invention chooses a quartz plate as substrate, and it is kept flat.Having the capable separator of certain thickness U with one then is placed on the quartz plate.Cover an onesize quartz plate more thereon.Under the relative position that keeps two quartz plates, they are fixed up at last.
Separator among the present invention can be that column type or cross section are the dielectric rod of rectangle, as shown in Figure 2.The material selection of sept can be born certain extruding and indeformable dielectric material.
Colloid micro ball suspension of the present invention splashes in the microcavity for preparing, and just forms the colloidal crystal of large-area single domain after the standing and drying on the one side in microcavity.
The present invention is by regulating the inclination angle of microcavity, can make tightr that the colloidal crystal that makes arranges.
The present invention does not have too meticulous requirement to the size of sept and the concentration of microballoon suspension, and regulating the two mainly is the total amount of regulating the microballoon in the microcavity, and then control grows the number of plies of ground colloidal crystal.
As the example of preparation two-dimensional colloidal crystal, (be of a size of between the 1.6cm * 2.5cm) and adopt copper wire (diameter is 0.5 millimeter), clamp the slide both sides, the formation microcavity with two clips as sept at two slides.With volumetric concentration is to leave standstill after 0.24% colloid micro ball suspension splashes into microcavity.The silicon dioxide microsphere diameter is 1.6 microns.The crystal growth time is generally a few hours, and as 2-6 hour, present embodiment was 3 hours.The control of silicon dioxide microsphere diameter is with reference to CN1470319A.
Fig. 5 is the local sector scanning electron microscope in centre (SEM) photo that the present invention adopts the two-dimensional colloidal crystal that diameter 1.6 micron silica microballoons make.Silicon dioxide microsphere is arranged in the close pile structure of hexagonal of high-sequential.By the indivedual point defects in the mapping, can directly see substrate confirm to be individual layer, the two-dimension periodic ordered structural crystal.
As the example of the three-dimensional colloidal crystal of preparation, (be of a size of between the 1.6cm * 2.5cm) and adopt copper wire (diameter is 1 millimeter), clamp the slide both sides, the formation microcavity with two clips as sept at two slides.With volumetric concentration is to leave standstill after 0.21% colloid micro ball suspension splashes into microcavity.The silicon dioxide microsphere diameter is 1.6 microns.The crystal growth time is 3 hours.
Fig. 6 is that to adopt diameter be the SEM photo on 1.6 microns the silicon dioxide microsphere accurate three-dimensional colloidal crystal surface of making in the present invention.Microballoon is arranged in ordered structure on the surface as can be seen.
Fig. 7 is that to adopt diameter be the section SEM observed result of the three-dimensional colloidal crystal made of 1.6 microns silicon dioxide microsphere in invention.It is two-layer to see that this crystal has, and the arrangement on section is orderly equally, proves the order of the three-dimensional colloidal crystal internal arrangement of the present invention's preparation.
Arrow g is illustrated under the gravity effect microballoon and begins closely to arrange in microcavity among Fig. 2, dry liquid level 2, the opening part arrow represents that solution begins the capillary secondary action microballoon of dry process from the microcavity opening direction and forms compact arranged face-centred cubic structure, and clip 1 is used for fixing two wave plates.
Claims (6)
1, a kind of two dimension, the preparation method of three-dimensional colloidal crystal, it is characterized in that in the space of one two dull and stereotyped parallel interval, be provided with three sealings, the microcavity system of one end opening, earlier the colloid suspension is injected in the microcavity, microcavity system opening is to oblique below then, because the gravity of microballoon is greater than the buoyancy of suspension to it, microballoon at first forms a unordered solid matter structure on a substrate of microcavity, utilize then colloid suspension in the microcavity from opening to the dry run of inside, be liquid level from the process that the aperture position of microcavity constantly moves inward, microballoon self-organizing and form ordered structure under its capillary secondary action.
2, the preparation method of a kind of two dimension according to claim 1, three-dimensional colloidal crystal is characterized in that the gradient of microcavity is controlled in 5 °.
3, the preparation method of two dimension according to claim 1, three-dimensional colloidal crystal is characterized in that at given composition colloidal crystal number of plies N, sept thickness D, microsphere diameter d, the turbid liquid volume concentrations of colloidal suspension C
vSatisfy:
In microcavity, make the colloid micro ball self-organizing form ordered structure by gravity and surface tension effects.
4, the preparation method of two and three dimensions colloidal crystal according to claim 1 is characterized in that adopting cylindrical or cross section is the dielectric rod of rectangle, and parallel being placed between two smooth substrates of flat board forms microcavity.
5, the preparation method of two dimension according to claim 3, three-dimensional colloidal crystal is characterized in that by regulating the inclination angle of microcavity, make tightr that the colloidal crystal that makes arranges.
6,, it is characterized in that the concentration of volume by regulating microcavity and colloid suspension controls the thickness of colloidal crystal according to the preparation method of claim 3 or 4 described two dimensions, three-dimensional colloidal crystal.
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| CN200410041939.9A CN1289180C (en) | 2004-09-10 | 2004-09-10 | Method for preparing two-dimensional or three dimensional colloid crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100391825C (en) * | 2005-10-20 | 2008-06-04 | 南京大学 | Non close parked metal hollow ball shell ordered network structure material and its making method |
| CN101270197B (en) * | 2008-03-12 | 2011-03-16 | 南京大学 | Method for preparing adjustable uniform hole polystyrene monolayer film |
| CN101717994B (en) * | 2009-12-03 | 2012-04-25 | 南京大学 | Method for preparing large-area single-domain two-dimensional colloidal crystal |
| CN101857381B (en) * | 2010-05-31 | 2012-01-25 | 河南大学 | Preparation method of polystyrene microsphere template and method for preparing zinc oxide thin film |
| CN105951168B (en) * | 2016-05-20 | 2018-08-17 | 中山大学 | Large area ABX3Type perovskite crystal film growth method and device |
| CN106192212B (en) * | 2016-07-03 | 2018-07-31 | 郑州轻工业学院 | A kind of preparation method of nano-cellulose based carbon fiber mesh non-woven fabrics flexible electrode |
| CN106245114B (en) * | 2016-07-14 | 2019-03-05 | 陕西师范大学 | A kind of growth form in the micro- reaction system of Flowing liquid and the controllable ultra-thin ABX of thickness3The method of perovskite monocrystalline thin slice |
| CN108004590A (en) * | 2017-12-12 | 2018-05-08 | 中国工程物理研究院激光聚变研究中心 | Nano-porous surface plasmon crystal and preparation method thereof |
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