CN1216678C - Capillary attration colloidal microball self-organization and two-dimensional, three-dimensional colloidal crystal preparing method - Google Patents
Capillary attration colloidal microball self-organization and two-dimensional, three-dimensional colloidal crystal preparing method Download PDFInfo
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- CN1216678C CN1216678C CN03131989.0A CN03131989A CN1216678C CN 1216678 C CN1216678 C CN 1216678C CN 03131989 A CN03131989 A CN 03131989A CN 1216678 C CN1216678 C CN 1216678C
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- 239000013078 crystal Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000011806 microball Substances 0.000 title claims description 29
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims description 39
- 239000000725 suspension Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 14
- 229920002223 polystyrene Polymers 0.000 claims description 14
- 238000001338 self-assembly Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011805 ball Substances 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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Abstract
The present invention relates to a colloidal microsphere self-organization under capillary attraction and a method for preparing two-dimensional colloidal crystal and three-dimensional colloidal crystal. A micro passage is arranged, so that a colloidal microsphere self-organization in the passage forms an ordered two-dimensional colloidal crystal and three-dimensional colloidal crystal by capillary attraction in the passage; the micro passage is a flaky passage. A cylindrical dielectric rod or a dielectric rod with a rectangular cross section is used and is placed between two smooth substrates in parallel to form a capillary passage. The present invention has no specific requirement to a peripheral atmosphere, has strong interference immunity and has no specific requirement to the concentration of a colloidal microsphere suspending liquid. The present invention has the advantages of simple technical process, short preparing period and high efficiency and can prepare single-domain two-dimensional colloidal crystal and single-domain three-dimensional colloidal crystal with large area, high quality and long-range order structure.
Description
One, technical field
The present invention relates to a kind of self-organizing of colloid micro ball and the preparation of colloidal crystal material, spontaneously suck in the microchannel by the suspension of capillary attraction exactly, prepare the method for two dimension, three-dimensional colloidal crystal by the self assembling process in the microchannel the monodisperse polystyrene colloid microballoon.
Two, background technology
To utilizing the research of the two and three dimensions colloidal crystal that monodispersed sub-micron colloid micro ball forms, not only have important scientific research value, and have important practical value.For example, can be used as the porous ceramics with specific function, porous metals, the porous magnetic material of template for preparing high-sequential.By colloidal crystal is template, introduces the intensity that loose structure can greatly improve pottery in block pottery.In addition,, make this class material can be used to prepare optical filter, optical switch, chemistry and biology sensor and optics integrated chip etc. because colloidal crystal has special optical diffraction characteristic and exists photon band gap.
Usually, the size of colloid micro ball is in micron or sub-micrometer scale, directly adopts manually-operated that microballoon is moved and they are arranged in three-dimensional close pile structure, and not only difficulty is big, and efficient is low.Existing multiple technologies can be assembled into colloidal crystal with colloid micro ball.The self assembling process that these technologies of preparing are often taken place under some specific function power by means of colloid micro ball.Summary is got up, and these methods can be divided into the deposition under the weight-driven, Coulomb repulsion self-organizing, extra electric field induction and deposition, compression molding techniques, vertical deposition 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 obtains, the thickness of crystal is restive, and manufacturing cycle is longer.Be not suitable for the colloid micro ball of those self gravitations greater than the buoyancy in suspension yet.
It is to rely on the electrostatic repulsion forces between the charged microballoon and form orderly structure that the Coulomb repulsion self-organizing obtains the colloidal crystal assemble method, referring to N.Ise, and Angew.Chem.Int.Ed.Engl.1986,25,323.This method except require microballoon charged, the colloid concentration in the strict control suspension of this method, otherwise obtain be likely body-centered cubic, face-centered cubic or unordered mixing phase in mutually.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, and 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.2002,12 693.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.
Fig. 1 C has shown the schematic diagram of vertical deposition method, referring to " Self assembly lights up, " J.D.Joannopoulos, Nature, 2001,414,257.Compare easier large tracts of land, the high-quality single domain colloidal crystal prepared with the technology of front.But it is high especially that this technology requires atmosphere on every side, and disturbance is also very responsive to external world.It can getablely be to contain a large amount of defectives even local unordered colloidal crystal that disturbance is arranged slightly.
Three, summary of the invention
Suspension is inhaled into the microchannel to the present invention seeks to utilize capillary force to drive down; The colloid micro ball self-organizing at liquid level top in the microchannel and form orderly arrangement in inside microchannels.
The present invention is provided with a minim channel, and with the capillary attraction in this passage, thereby the colloid micro ball self-organizing forms orderly two dimension, three-dimensional colloidal crystal structure in passage.Minim channel is a book sheet passage.
Invention has been adopted by place sept between two plain films such as sheet glass, forms a microchannel identical with sept thickness; End with the microchannel is immersed in the suspension of colloid micro ball then.Its top takes place in water evaporates in the microchannel.For the moisture that is evaporated in the compensating pipe, suspension can be inhaled into from the lower end of microchannel in the pipe, and this has just formed a water movement from the bottom to top, is driving colloid micro ball simultaneously together to tip motions.After colloid micro ball outreached, its motion was restricted.These microballoons finally form close pile structure on the top of microchannel according to the minimum principle of system capacity.Through promptly preparing the single domain colloidal crystal of required size behind the reasonable time.Plain film is also as slide, book sheet etc.
The present invention is applicable to the colloid micro ball to arbitrary dimension; Be applicable to charged and neutral colloid micro ball.
By sept thickness in the control microchannel, can very conveniently get the thickness of accurately controlling colloidal crystal among the present invention.
The diameter d of given colloid micro ball, composition colloidal crystal number of plies N among the present invention be not in order to grow the colloidal crystal that the number of plies is N+1, the thickness H of microchannel in the microchannel
NMust satisfy:
The present invention does not have specific (special) requirements to surrounding atmosphere; Strong interference immunity; Concentration to the colloid micro ball suspension does not have specific (special) requirements.
The technology of the present invention technology is simple, and manufacturing cycle is short, and the efficient height can be prepared large-area, high-quality single-domain two-dimensional and three-dimensional long range ordered structure colloidal crystal.
Four, description of drawings
The invention will be further described below in conjunction with accompanying drawing and by 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.About the detailed content of these technology, see relevant document.
Fig. 2 is a constructional device schematic diagram of the present invention.Water movement direction 6 in clip 1, slide 2, sept 3, container 4, colloid bead suspension 5, the interlayer.Bead forms orderly ordering structure 7 in the upper end.
Fig. 3 adopts regional area SEM (SEM) photo of the two-dimensional colloidal crystal that the monodisperse polystyrene microsphere of 1.5 microns of diameters makes for the present invention.
Fig. 4 adopts the fringe region SEM photo of the two-dimensional colloidal crystal that the monodisperse polystyrene microsphere of 1.5 microns of diameters makes for the present invention.
Fig. 5 adopts the SEM photo on the three-dimensional colloidal crystal surface that the monodisperse polystyrene microsphere of diameter 650 nanometers makes for the present invention.
Fig. 6 adopts the section SEM photo of the three-dimensional colloidal crystal that the monodisperse polystyrene microsphere of diameter 650 nanometers makes for the present invention.
Three-dimensional colloidal crystal surface and cross-section morphology SEM photo that Fig. 7 adopts the monodisperse silica microspheres of diameter 500 nanometers to make for the present invention.
Five, the specific embodiment
The present invention is by the process of self-organization of the colloid micro ball under the capillary attraction in the microchannel, prepares high-quality two and three dimensions colloidal crystal.Implementation method is seen Fig. 2.Dimension mark is arranged on the photo.Can grow polystyrene colloid microballoon, silicon dioxide colloid microballoon and various composite dielectric body colloid micro ball.
The present invention chooses a wave plate as substrate, and it is kept flat.Then with two identical, have that certain thickness separator is parallel to be placed on the wave plate.Cover an onesize wave plate more thereon.Under the relative position that keeps two wave 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.Clip 1 is in order to fix two slides 2, sept 3, container 4 dress colloid bead suspensions 5.Water movement direction drive bead moves together in the interlayer, moisture is from slide upper end start vaporizer, and bead forms orderly ordering structure in the upper end simultaneously, and water enters interlayer and goes compensation from the upper end moisture evaporated from the slide lower end, meanwhile, the bead in the suspension also has been brought in the interlayer.
The present invention also can adopt monodispersed silica spheres as sept.Distance between two wave plates equals the silica bulb diameter.
The present invention is immersed in an end of prepared microchannel in the colloid micro ball suspension that configures., after needed size, the microchannel is proposed from suspension in colloidal growth.Finally prepare the colloidal crystal of large-area single domain.
The present invention implements to stir to the colloid suspension in the process of colloidal crystal growth simultaneously, can prevent that like this in the long-time growth course of crystal colloid micro ball from depositing to the bottom of suspension.
Colloidal crystal is to grow in the microchannel that forms between the substrate that two relative positions are fixed among the present invention.The stirring of suspension does not influence the growth of crystal among the present invention.
As the example of preparation two-dimensional colloidal crystal, (be of a size of between the 1.6cm * 2.5cm) and adopt silica spheres (diameter is 1.8 microns) as sept, clamp the slide both sides with two clips, forming a thickness is 1.8 microns microchannels at two slides.Preparation colloid micro ball suspension is 15mL, and the capacity of putting into is the crucible of 20mL, carries out magnetic and stirs.The polystyrene microsphere diameter is 1.5 microns.The crystal growth time is 8 hours.
Fig. 3 is the local region S EM photo in centre that the present invention adopts the two-dimensional colloidal crystal that 1.5 microns polystyrene microspheres of diameter make.Polystyrene microsphere is arranged in the close pile structure of hexagonal of high-sequential.
The two-dimensional colloidal crystal edge regional area SEM photo that Fig. 4 adopts 1.5 microns polystyrene microspheres of diameter to make for the present invention.From figure, 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 silica spheres (diameter is 1.8 microns) as sept, clamp the slide both sides with two clips, forming a thickness is 1.8 microns microchannels at two slides.Preparation colloid micro ball suspension is 15mL, and the capacity of putting into is the crucible of 20mL, carries out magnetic and stirs.The polystyrene colloid microsphere diameter is 650 nanometers.The crystal growth time is 12 hours.
It is the SEM photo on the polystyrene microsphere of the 650 nanometers three-dimensional colloidal crystal surface of making that Fig. 5 the present invention adopts diameter.Microballoon is arranged in ordered structure on the surface as can be seen.
Fig. 6 is that to adopt diameter be the section SEM observed result of the three-dimensional colloidal crystal made of the polystyrene microsphere of 650 nanometers in invention.Can see that this crystal has three layers, the arrangement on section is a long-range order equally, proves the three-dimensional colloidal crystal internal arrangement long-range order of the present invention's preparation.
As the example of the three-dimensional colloidal crystal of preparation, (being of a size of and adopting thickness between the 1.6cm * 2.5cm) is 9.0 microns sept, the microchannel of formation at two slides.Fig. 7 is that to adopt diameter be the surface and the section SEM observed result of the three-dimensional colloidal crystal made of the silicon dioxide microsphere of 500 nanometers in invention.Can see that this crystal has 24 layers, the long-range order on the section shows the three-dimensional colloidal crystal internal arrangement long-range order that the present invention prepares.
Claims (7)
1, the colloid micro ball self assembly under a kind of capillary attraction prepares the method for two dimension, three-dimensional colloidal crystal, it is characterized in that being provided with one by the capillary channel that constitutes width 500 nanometers-9 micron between two smooth substrates, capillary channel is immersed in the microballoon suspension, utilize the interior capillary force of passage that suspension is drawn in the capillary channel, colloidal crystal is grown by process of self-organization on the top of the inner fluid column of capillary channel, thereby the colloid micro ball self-organizing forms orderly two dimension, three-dimensional colloidal crystal structure in passage.
2, the method that is prepared the two and three dimensions colloidal crystal by the described self assembly of claim 1 is characterized in that adopting cylindrical or cross section is the dielectric rod of rectangle, parallelly is placed between two smooth substrates the capillary channel of formation.
3, the method that is prepared the two and three dimensions colloidal crystal by the described self assembly of claim 1 is characterized in that adopting single decentralized medium ball as sept, is placed between two smooth substrates, forms capillary channel.
4, the method that is prepared the two and three dimensions colloidal crystal by the described self assembly of claim 1 is characterized in that in crystal growing process the colloid micro ball suspension being stirred, and makes that the colloid concentration of suspension is in uniform state in the crystal growing process.
5, the method that is prepared the two and three dimensions colloidal crystal by claim 1 or 2 described self assemblies is characterized in that controlling by the thickness of regulating capillary channel the thickness of colloidal crystal.
6, the method for preparing the two and three dimensions colloidal crystal by claim 1 or 2 described self assemblies, the polystyrene colloid microballoon that it is characterized in that growing, silicon dioxide colloid microballoon and various composite dielectric body colloid micro ball.
7, the method that is prepared the two and three dimensions colloidal crystal by the described self assembly of claim 1 is characterized in that the number of plies N of microballoon in colloid micro ball diameter d, the colloidal crystal, the spacing H between composition two substrates capillaceous
NSatisfy:
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CN100465345C (en) * | 2006-04-12 | 2009-03-04 | 南京大学 | Surface plasmon crystal and preparation method thereof |
CN100579895C (en) * | 2007-10-24 | 2010-01-13 | 南京大学 | Method for preparing two-dimension square colloidal crystal |
CN101270197B (en) * | 2008-03-12 | 2011-03-16 | 南京大学 | Method for preparing adjustable uniform hole polystyrene monolayer film |
CN101597786B (en) * | 2009-07-02 | 2012-05-23 | 中国科学院物理研究所 | Device and method for preparing colloidal crystal simple layer film |
US20120282682A1 (en) * | 2009-11-02 | 2012-11-08 | Ffei Limited | Micro-channel structure method and apparatus |
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 |
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CN104096609A (en) * | 2014-07-21 | 2014-10-15 | 东南大学 | Colloidal crystal paper chip and preparation method |
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