Bottom-Up Strategy Using Superwettability for the

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Hybrid Top–down/bottom–up Strategy Using Superwettability for the Fabrication of Patterned Colloidal Assembly Yuezhong Wang, Cong Wei, Hailin Cong, Qiang Yang, Yuchen Wu, Bin Su, Yong Sheng Zhao, Jingxia Wang, and Lei Jiang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b11945 • Publication Date (Web): 29 Jan 2016 Downloaded from http://pubs.acs.org on January 30, 2016

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ACS Applied Materials & Interfaces

Hybrid Top–down/bottom–up Strategy Using Superwettability for the Fabrication of Patterned Colloidal Assembly ＃

Yuezhong Wang1,2 , Cong Wei,3

＃

Hailin Cong1,* Qiang Yang3, Yuchen Wu3, Bin Su3,

Yongsheng Zhao,3 Jingxia Wang2*, and Lei Jiang2 Prof. Hailin Cong, Dr. Yuezhong Wang, 1

Laboratory for New Fiber Materials and Modern Textile, Growing Base for State

Key Laboratory, Qingdao University, Qingdao, China, 266071 Prof. Jingxia Wang, Prof. Lei Jiang, Dr. Yuezhong Wang 2

The Laboratory of Bio–inspired Smart Interface Sciences, Technical Institute of

Physics and Chemistry, Chinese Academy of Science, Beijing, China, 100190 E–mail: [email protected] Prof. Yongsheng Zhao, Prof. Bin Su, Dr. Cong Wei, Dr. Yuchen Wu, Dr. Qiang Yang, 3

Beijing National Laboratory for Molecular Sciences, Key Laboratory of

Photochemistry, Key Laboratory of Organic Solids, Key Laboratory of Green Printing, Institute of Chemistry,Chinese Academy of Sciences, Beijing 100190, China ＃

Yuezhong Wang and Cong Wei contribute equal to the article.

KEYWORDS: colloidal assembly, top–down/bottom–up, optic waveguide

pattern

colloidal,

superwettability,

ABSTRACT. Superwettability of substrate has aroused profound influence on the production of novel and advanced colloidal assembly in recent decades owing to its effect on the spreading area, evaporation rate, and the resultant assembly structure. In this paper, we investigated a detailed influence of the superwettability of transfer/template

substrate

on

the

colloidal

assembly

ACS Paragon Plus Environment

from

hybrid


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Top–down/bottom–up strategy. By taking advantage of a superhydrophilic flat transfer substrate and a superhydrophobic groove–structured silicon template, the patterned colloidal microsphere assembly was formed including linear, mesh–, cyclic– and multi–stopband assemblies arrays of microspheres, and the optic–waveguide of circular colloidal was demonstrated. We believed this liquid top–down/bottom–up strategy would open an efficient avenue for assembling/integrating microspheres building blocks into device applications in a low–cost manner. 1. INTRODUCTION Superwettability1–6 has produced many important applications in anti–wetting materials,7 anti–icing, oil–water separation,8 chemical reactions,9–10 directional water collection11,

low–energy–consuming

frosting

prevention,12

subcooled

water

non–stickiness,13 condensation heat and mass transfer enhancement,14–20 and pattern crystals.21–48 Particularly, superwettability of substrate has aroused a profound influence on the production of novel and advanced colloidal assembly in recent decades22–48 owing to its effect on the spreading area, evaporation rate and the resultant assembly structure. Typically, superhydrophilic substrate25–30 (with water contact angle (CA) approaching 0o) benefits the fully wetting/spreading of colloidal suspension, which promotes the formation of continuous and high–quality colloidal assembly. In contrast, low–adhesive superhydrophobic substrate (with water CA >150o) has been known as a specific substrate to fabricate the colloidal assembly with unique properties.31–33 For example, its low–adhesive property results in a continuously receded three phase contact line (TCL) during solvent evaporation procedure, which induces the formation of spherical colloidal assembly32,33 or crack–free colloidal crystals with narrow stopband.31 It is worth to be noted that the combination of hydrophilic/hydrophobic substrate produces an effective approach for the creation of patterned colloidal microsphere assembly.40–42 Wherein, the hydrophilic part is beneficial for the latex assembly owing to the pinning TCL,34–37 while the hydrophobic part prevents from the assembly owing to its receding


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TCL.38–40 Recently, some novel approaches are developed for the patterned colloidal microsphere assembly based on the modulation of substrate wettability.44–49 For example, Song et al. inkjet–printed series of pattern colloidal by smartly designing the pattern from hydrophobic region surrounded by hydrophilic point.44,45 Su et al.46–49 developed a novel assembly approach for the pattern with precise orientation and position based on the elaborate design of wet and de–wet region by the sandwiching the latex suspension in between the template and transfer substrate. In this case, the assembly pattern can be directly transferred to the desired substrate, it is convenient for the further device application of the as-prepared pattern array. In contrast, for the traditional template assembly method

50–54

the latex particles can be easily and

precisely assembled on the template in large scale and suitable time, but the necessary pattern transfer or template removal is required for the further device applications. Accordingly, the newly-developed sandwich assembly approach46-49 provide a simple and direct assembly

approach for

the pattern array on the desired substrate,

completely avoiding the additional substrate transfer process. In this paper, we demonstrated a full investigation of the influence of the superwettability of template/transfer substrate on the patterned colloidal microsphere assembly through extending above–mentioned sandwich method. By taking advantage of a superhydrophilic flat transfer substrate and a superhydrophobic groove–structured silicon template, the well–ordered pattern colloidal was formed, including linear, mesh–, cyclic– and multi–stopband assemblies arrays of microspheres. The optic–waveguide behavior of circular colloidal was investigated. We believed this liquid top–down/bottom–up strategy would open an efficient avenue for assembling/integrating microspheres building blocks into device applications in a low–cost manner. 2. EXPERIMENTAL SECTION

Groove–structured silicon templates. The silicon wafers with template (N doped, oriented, 400 µm thick, 10 cm diameter) were structured by direct laser



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writing apparatus (DWL200, Heidelberg Instruments Mikrotechnik, Germany) that transferred the computer–predefined design onto the photoresist (Shipley Microposit S1800 series)–coated wafer with about 1 µm precision. After irradiation and development, the wafers were etched using deep reactive ion etching (DRIE, Alcatel 601E) with fluorine–based reagents for different times (10 s to 6 min) depending on the desired height of the structures. Groove–structured silicon substrates with groove width of 5 µm, gap of 5 µm, and height of 20 µm were fabricated. After resist stripping (Shipley Microposit Remover 1165), the substrates were cleaned with ethanol and acetone prior to use.

Preparation

of

Polystyrene–methyl

methacrylate–arylic

acid

(poly(St–MMA–AA) ) microspheres. The monodispersed latex particles of poly(St–MMA–AA) were prepared by modified emulsion polymerization based on our previous method59. Firstly, aqueous solution of

sodium dodecyl benzene

sulfonate (0–0.072 mM) and ammonium bicarbonate (6.30 mM), and monomer mixture of methyl methacrylate (MMA,10.00 mM ), acrylic acid (AA,13.89 mM) and styrene (St,182.60 mM) were added into a four–necked flask. Subsequently,

the

above mixture was stirred at 70℃ for 10 h after charging the initiator of ammonium persulfate. The as–prepared latex particles can be used directly without purification. The fluorescent latex was obtained based on the similar procedure except charging the fluorescent molecule such as coumarin 6 (about 1% wt of St) into the monomer system.


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Surface modification for groove–template and glass substrate. The hydrophobic treatment groove–template or substrate were generated by silanizing the template/substrates

with

heptadecafluorodecyltrimethoxysilane

(FAS)

in

a

decompression environment at room temperature for 0.5 h and then heated at 80°C for 0, 1, 2 and 3 h respectively, yielding different hydrophobic surfaces. The superhydrophobic templates were obtained by combining the low-surface energy treatment with surface roughness structure after being FAS modified for longer than 3 h. Superhydrophilic glass and silicon wafer substrate were obtained by oxygen plasma treatment. The relevant operating parameters are as follows: feed gas is oxygen; gas flow is 40 SCCM; backing vacuum degree (working pressure) is 40 Pa; discharge power (working power) is 200 W; working time is 10 min). The water CA of the treated substrate is ca. 0°. And that of the clean silicon wafer is 33.5° ± 4.2°.

Generation of pattern colloidal from hybrid Top–down/bottom–up approach. A FAS modified groove–structured silicon substrate with groove width of 5 µm, gap of 5 µm, and height of 20 µm was held horizontally. Then poly(St–MMA–AA) latex the colloidal suspension’s weight concentration of 8.67%, see Figure S7–S8 for the influence of the colloidal concentration on assembly structure) was carefully dropped onto the template and covered by a flat substrate, yielding a sandwich assembly. Keeping the assembly system at 20o for 12 h, long poly(St–MMA–AA) microspheres linear assemblies were achieved. In this case, controlling the gap between the chosen substrate and the groove–structured template at ca. 20 µm led to continuous liquid stripes. The assembly process for other pattern colloidal was similar except changing



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the kind of templates. The two or multi- stopband assembly array was obtained by repeating above-mentioned assembly process except using as-prepared the assembly array as the transfer substrate. Characterization. The morphology of groove–structured silicon substrates and aligned pattern colloidal assemblies were investigated by scanning electron microscopy (SEM, JEOL, JSM–7500F, Japan) at an accelerating voltage of 5.0 kv. Bright–field optical images and fluorescence microscopy images were taken by system microscopy (Olympus BX51, Japan), by exciting the samples with a mercury lamp. The single composite microring was locally excited by a focused 400 nm pulse laser beam (200fs, 1000Hz). The oxygen plasma instrument (DT–03) is purchased from Suzhou OPS oxygen plasma Technology Co., Ltd. Static CAs were measured on a DataPhysics (Germany) OCA20 contact–angle system at ambient temperature. The adhesion force is characterized by adhesion force tester of DCTA21 machine, which was made in Germany by dataphysics instruments Gmbh. The average CA was obtained by measuring more than five different positions of the sample. Calculation of the ordering of the latex assembly. The quantative analysis of the ordering of latex assembly is according to the literature method.55 The detailed calculation process includes transferring SEM Micrograph into a binary image, and locating the centroid of each particle via using the MATLAB image processing toolbox. The curves of g(r) were calculated between r = 0.05R0 to r = 30R0 using shell thicknesses of 0.016R0, where R0 is the particle radius and r is the distance from the origin of the radial distribution function and g(r) is the calculated distance. Each SEM image was measured against a perfect array with comparable period, image resolution, and number of particles. RESULTS AND DISCUSSION


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Scheme 1 showed the fabrication process of linear colloidal assembly from hybrid Top–down/bottom–up approach. Firstly, the milky poly(St–MMA–AA) latex (5 µl, the colloidal suspension’s weight concentration is about 8.67%, Figure S7 presents the influence of colloidal concentration on assembly structure) was sandwiched

into

a

superhydrophobic

groove–structured

template

and

a

superhydrophilic flat transfer substrate (glass or silicon wafer, oxygen plasma processing 10 min, working power is 200 W). Copper wires with diameter of 20–100 µm were employed to control the gaps between the substrate and groove–structured template. Keeping the assembly system at constant humidity/temperature for 12 h, the linear assemblies with precise position can be generated. In this process, the key step is to control the size of the gaps between the transfer substrate and the groove–structured template. Only an appropriate gap is favorable for producing a confined effect of the latex film between the substrate and template. Specifically, the large gap will weak the rupture behavior of the liquid film, resulting in a continuous film rather than patterned colloidal microsphere assembly on the substrate. Furthermore, the superhydrophobic template is almost completely clean after being transfer and it can be reused immediately as shown in Figure S3.



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Scheme 1. Schematic illustration for the general strategy to align poly(St–MMA–AA) latex in one direction based on a sandwich assembly. (a, b) Colloid latex was carefully dropped onto the super–hydrophobic groove–structured template and covered by a flat superhydrophilic transfer substrate, yielding a fixed–gap sandwich assembly system. The assembly system was put at constant template/humidity for 12 h. (c) Schematic of the contact position for the colloid latex between the superhydrophobic template and superhydrophilic transfer substrate, the insert is the shape of the water droplet on the transfer substrate and the template respectively. (d) With the evaporation of solvent, the groove wall array served as wetting defects to control the rupture of colloid latex, yielding a micrometer–scaled liquid film between the substrate and the top surface of groove wall. Such a liquid bridge provides a gradually reducing confined space for latex aggregation. (e) An close–packed, linear assemblies arrays of colloids can be formed upon the substrate. (f) After removal of the groove–structured template by physical peeling, a precisely positioned colloidal assembly pattern can be generated.

Figure 1 demonstrated the optical microscopy images and SEM images of as–prepared

patterned

colloidal

microsphere

assembly

from

hybrid

Top–down/bottom–up approach. Clearly, linear colloidal assembly with structure color of red, green and blue were showed in Figure 1a–c respectively. The line length approaches 0.5 cm and the adjacent spacing between two lines is ca. 4.0 µm in Figure 1a–c. Wherein, poly(St–MMA–AA) microspheres were assembled into linear


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microstructures aligned in one direction at precise positions (Figure 2a). Top width (3.9 ± 0.5 µm) of the colloidal assembly line is more narrow than that of the bottom one (6.6 ± 0.8 µm) (Figure 2a), which is affected by the gap between the template and the substrate as shown in Figure S6. The poly(St–MMA–AA) microspheres exhibited hexagonal close–packed structure on the top of the colloidal assembly line, showing iridescent structure color. Importantly, when further replacing the template with well–designed mesh and cyclic pattern, the large–scale colloidal assembly with the correspondingly pattern can be fabricated in Figure 1d–f. As–prepared patterned colloidal microsphere assembly shows iridescent structure color owing to the well–ordered latex assembly in inserted image. Accordingly, this hybrid Top–down/bottom–up approach provides a high–throughput and precise strategy to produce guided microspheres pattern assembly. In this way, we can precisely control the shape, location, and area of the colloidal assembly in one step, omitting the process of removing the template and transferring to the substrate.



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Figure 1. Optical microscopy images and SEM images (inserted) of pattern latex assembly from the hybrid Top–down/bottom–up approach. (a) blue, (b) green, (c) red linear colloidal, (d) mesh colloidal, (e, f) cyclic colloidal. As–prepared latex assembly shows homogeneous structure color arousing from the well–ordered latex arrangement, that can be clearly confirmed from the inserted SEM images. The inserted image of right–top is the optic microscopic images, and the inserted image of left–bottom are the SEM images of the corresponding samples.

The wettability of the groove–shaped template produces an important impact on the resultant latex assembly in Figure 2a–d. Evidently, a distinct pattern morphology and latex assembly were observed when changing the wettability of the template. As shown in Figure 2a, a perfect and smooth linear colloidal with well–ordered latex arrangement was obtained on the superhydrophobic template. In contrast, an increased defect formed on the lineal colloidal in Figure 2b–d when the sample was assembled using the less hydrophobic template. The increased hydrophilicity of template induced an obvious growth of the defect area when the CA of the template changed from 147.7° ± 4.5°, to 103.5° ± 5.6°, to 72.7° ± 3.8°, and to 4.2° ± 2.5° as shown in Figure 2a, 2b, 2c and 2d respectively. Concretely, only somewhat disordered assembly of microparticles can be observed in Figure 2b (103.5° ± 5.6°) comparing that in Figure 2a (147.7° ± 4.5°). The sample from template with CA of 72o (Figure 2c) showed more peeling and disordered structure, which indicates a degraded latex ordering in the samples when improving the hydrophilicity of the template. What’s the most worse, large part of blank region can be observed for the sample from hydrophilic template (with water CA of 4.2° ± 2.5°) in Figure 2d. It implies that most of latex particles cannot be effectively transferred to the substrate or plenty of latex particles


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will be infiltrated/remained in the groove–structure of the template as shown in Figure S4d. Accordingly, the successful fabrication of the line structure in Figure 2a can be evaluated as a well–ordered latex assembly and complete transfer of the structure from template to the substrate. These can be attributed to the synergistic effect of superhydrophobic template and superhydrophilic transfer substrate. In this case, the low adhesion force (Figure S2 for the adhesion force of the template) of the superhydrophobic template can prevent latex from infiltration or adhesion into the groove template (in Scheme 1c),31 which is favorable not only for the easily peeling procedure of the template from the substrate but also its recycle use, contributing to the complete transfer and smooth assembly surface. Vice verse, increasing the hydrophilicity of template promotes the spreading and infiltrating of the latex into the groove structure of template, resulting in more particles contacting with template

as

shown in Figure S4. The case is corresponding to the increased defect area resulted from increased hydrophilicity of the template in Figure 2d. Otherwise, the combination of superhydrophobic groove template and superhydrophilic transfer substrate provides an effective platform for well–ordered latex assembly owing to its slow evaporation time and additional assembly force from the sliding TCL during solvent evaporation process.31



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Figure 2. SEM images of the pattern latex assembly from (a–d) groove–structured template with water CA of (a) 147.7° ± 4.5°, (b) 103.5° ± 5.6°, (c) 72.7° ± 3.8°, (d) 4.2° ± 2.5° combining with the superhydrophilic transfer substrate. The inserted left–bottom in (a–d) is the FFT transfer of the corresponding SEM image of as–prepared samples. (e–g) SEM image of the latex assembly on the glass substrate with water CA of (e, f) 33.4° ± 2.4°, (g) 105.6° ± 4.2° combining with superhydrophobic template. (h, i) SEM images of the latex particles leaving on the superhydrophobic template when combining hydrophobic transfer substrate. The photograph of the inserted right top is the shape of water droplet on the as–using groove template (a–d), and on the transfer substrate (e, g). The superhydrophobic template combined with superhydrophilic transfer substrate is the optimal choice for the well–ordered latex assembly and perfect transfer.

On the other hand, the wettability of transfer substrate affects the resultant latex assembly as well. Figure 2e and g presented SEM images of the as–prepared samples from transfer substrate with different wettability combining with superhydrophobic template. Transfer substrate with lower water CA is favorable to an increased transfer of the latex particles onto the substrate in Figure 2e, while increased water CA leads to little particles being transferred in Figure 2g, suggesting that the latex particles prefer to keep in the groove template in Figure 2(h and i) for the transfer substrate


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with higher CA. Interestingly, when using superhydrophobic template, most of microspheres leaves on the top of the groove–structured template rather than infiltrated into the internal of the groove template as shown in Figure 2h and i, which also implies that superhydrophobic groove–structured template prevents the latex from infiltration into the interior of the template. Accordingly, a combining use of superhydrophobic template and the superhydrophilic transfer substrate is the most optimal choice for the perfect latex assembly though hybrid Top–down/bottom–up approach.

Figure 3. (a–e) Curves of g(r) calculated for pattern latex assembly (a) with perfect array and samples fabricated from groove template with wettability of (b) 147.7° ± 4.5°, (c) 103.5° ± 5.6°, (d) 72.7° ± 3.8°, and (e) 4.2° ± 2.5°, combining with the superhydrophilic transfer substrate respectively. Insert images from (a–e) are the corresponding Fourier transforms (FT) transfer in 2D way of latex assembly from the corresponding template. (f–i) Single–sided power spectra FT of g(r)–1 compared to that of the corresponding perfectly ordered arrays for the samples obtained from template with wettability of (f) 147.7° ± 4.5°, (g) 103.5° ± 5.6°, (h) 72.7° ± 3.8°, (i) 4.2° ± 2.5° combining with the superhydrophilic transfer substrate. The power spectra were scaled to



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have identical maximal at f/f0 = 1. Inserted images in the (f–i) are the corresponding SEM images of the latex assembly.

To understand the influence of the substrate wettability on the latex assembly, we conducted a quantitative analysis in Figure 3 for the ordering of the linear colloidal arrays obtained from different wettability template (Figure 2a–d). The ordering of the latex assembly can be evaluated by calculating the linear colloidal pair correlation function, g(r), given in Equation (1) according to the literature method,55 g(r) =

1 dn (r , r + dr ) ρ da (r , r + dr )

Where a is the shell area and n(r, r+dr) is the number of particles that lies within the shell considered. As shown in Figure 3a, g(r) shows a series of broad peaks that coincides with those calculated for a perfect array. The peak intensities of g(r) decreases under the different samples, indicating that the 2D ordering decreases. The linear colloidal arrays obtained by superhydrophobic groove–structured template exhibit significant correlation in Figure 3b beyond the tenth normalized distance r/2R0 comparing that the perfect array in Figure 3a, indicating its perfect well–ordered structure. While samples from the other cases show little corresponding to the perfect array. Furthermore, a quantitative measure of ordering can be evaluated by the value (k/k0) of the full width at half maximum (FWHM) based on literature method23,24 to quantitatively investigate the wettability influence on latex assembly. k/k0 is the first peak in the Fourier transform of the function g(r)–1 of the sample and that of a perfectly ordered array respectively. Figure 3f–i demonstrated k/k0 values calculated for samples prepared from template with different wettability. The value of sample


(1)

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from template with water CA of 147.7° ± 4.5° (Figure 2a) and 103.5° ± 5.6°(Figure 2b) are 1.17 and 1.24 respectively (Figure 3f and g), which indicates that the poly(St–MMA–AA) arrays from these substrate are highly ordered.57–59 In comparison, the k/k0 values, calculated for samples prepared from template with water CA of 72.7° ± 3.8° (Figure 2c) and 4.2° ± 2.5° (Figure 2d) curves are 2.06 and 2.94 respectively (Figure 3h and i), implying that the latex assembly are highly disordered.56–59 The decrease of k/k0 of latex assembly from the template substrate with higher water CA confirms that the combination of superhydrophobic template with superhydrophilic substrate is favorable for the efficient latex assembly and transfer.

Figure 4. (a–c) Optic microscopy images (in top–view way) and (d–f) the corresponding schematic illustration for the in–situ observation of the formation process for linear colloidal assembly (in cross–section view). (a, d) The initial state of the poly(St–MMA–AA) latex in the sandwich assembly system. (b, e) assembled process, the latex film retraction line is indicated by red arrows. (c, f) complete microspheres assembly.



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To explore the growing details of aligned linear latex assembly, Figure 4a–c presented in–situ assembly procedure of linear assembly monitored by video recording through an optical microscope in a top–view way. Figure 4d–f schemed the detailed assembly process in a cross–view. Owing to a suitable gap presents between the groove tops and the glass plate, a poly(St–MMA–AA) latex film (Figure 4a and d) can form. Following the evaporation of water at the edges of this sandwich system, the gas–solid–liquid TCL of poly(St–MMA–AA) latex underwent unidirectional shrinkage in Figure 4b and e. Since the ordered groove tops pinned and dominated the rupture of the liquid films, an array of ca. 5 µm width parallel to liquid bridges was formed (Figure 4c and f). In contrast to cylindrical liquid bridges suspended in air,34–55,59 three–dimensional (3D) liquid bridges with a meniscus in both the horizontal and vertical directions are formed in between groove tops and substrate owing to the superhydrophobic nature of not only the top substrate but also the neighboring groove–wall. In this case, poly(St–MMA–AA) microspheres are restricted following by the shrinkage of the 3D liquid bridges, yielding trapezoid–shaped linear assemblies in Figure 4f with gradually reducing number of microspheres from bottom to top as shown in Figure S5 and S6. In brief, the ordered groove–walls dominated in guiding the rupture of the latex and formed an array of parallel liquid bridges, yielding an array of regularly microspheres linear assemblies (Figure 4e and f). It should be pointed out that these used templates can be recycled by a simple organic solvents washing process to get rid of deposited microspheres.


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Figure 5. Schematic illustration for the preparation of (a, b) pattern colloidal with double bandgap, (c) heterogeneous colloidal arrays and (g) dot–line composite structure. Optical photograph (d) and SEM images (e, f) of the heterogeneous colloidal arrays. (h–j) SEM images of heterogeneous dot–line colloidal arrays with different magnification.

The developed method is versatile for creating the heterogeneous film besides for linear colloidal assembly. Figure 5 shows the schematic of pattern colloidal with double bandgap as shown in Figure S8 using a two–step procedure. In this case, the as–prepared linear colloidal was used as the transfer substrate, which sandwiched the milky poly(St–MMA–AA) latex in a direction orthogonal to the initial stamp orientation combining with the groove–template. After solvent evaporation, heterogeneous linear colloidal were obtained, which showed two different uniform colors due to light diffraction. These iridescent color mainly depended on the two kinds of size of the microspheres and the refractive indexes, suggesting the well–ordered latex assembly. The magnified SEM images of a crossover of two lines of crystal films (Figure 5e and f) displays the heterogeneous structures of colloidal



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assembly; one line is made of 223 nm microspheres, and the other is made of 264 nm microspheres (the colloidal suspension’s weight concentration is about 8.34%, see Figure S8). Some microspheres residue between the two lines of crystal film possibly because the first step colloidal lines can also be pinned and dominated the rupture of the liquid films. The gap between the groove tops and the linear colloidal substrate can not be uniform during the second printing process due to the thickness of the primary patterned crystal. From Figure 5f, we could observe that no microspheres (264 nm) appeared on the primary linear patterned crystal film made of microspheres (223 nm) after the second assembly process, which suggests that the interaction between the two microspheres is smaller than the liquid film shrink traction. Some interesting phenomenon can be observed from Figure 5g–j. Dot–line composite structures can be obtained by reducing the poly(St–MMA–AA) latex concentration (the colloidal suspension’s weight concentration is about 4.17%). The dots were assembled on the top of the line rather than between the neighboring lines, because the latex prefers to assembly at the lower gap region.


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Figure 6. Microring colloidal and its waveguide property. a) Fluorescence optic microscopy images and b) fluorescent spectrum of microrings colloidal. (c) Schematic illustration of optical waveguiding along microring–patterned after irradiated by laser. A laser beam was focused on the microring to investigate the optical propagation. (d) Photoluminescence (PL) images of microring–pattern under a focused 400 nm laser beam F excitation. The excitation positions are marked with the red circles.

Waveguide behavior is a typical property for the determination of optic manipulation and the transport.48,60,61 To demonstrate the waveguide property of the patterned colloidal microsphere assembly, we fabricated the circular colloidal by using the micro–ring template and the P(St–MMA–AA) latex containing of fluorescent coumarin 6 according to the Scheme 1. Figure 6 shows the microscopic optic images of the as–prepared microring assembly. The as–prepared microring has the interior and exterior diameter of 20 and 26 µm respectively, with the ring width of 3 µm respectively. The microrings showed homogeneous bring–green color in Figure 6a owing to the fluorescent signal. The latex particles are well–ordered assembled in the circular as inserted in Figure 6a, indicating the good optic manipulation behavior. The



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waveguiding behavior of these microrings was investigated using far–field microscopy and spectroscopy,60,61 as shown in Figure 6c. When focused a continuous wave laser onto one position of the microring (Figure 6c), the generated photoluminescence was strongly guided by the regularly arranged structure, causing the light to propagate through the colloidal microrings wall. This optic waveguide behavior can be fully confirmed in Figure 6d. A shinning blue signal is observed around the whole microring after a laser beam focused on one point of the microring. Meantime, a obvious fluorescent spectrum can be captured from the microring as shown in Figure 6b. 4. CONCLUSION

In summary, we have reported a simple fabrication approach toward patterned colloidal including linear–, mesh–, circle– and multi–stopband pattern colloidal from the hybrid Top–down/bottom–up approach. Where, the effective control of the template/transfer substrate wettability produces a decisive role on the final latex assembly. By combining the superhydrophobic template and superhydrophilic transfer substrate, high–quality latex assembly can be achieved, and the basic optic waveguide test was carried out for the circular assembly. We anticipated that this fabrication approach will become a useful platform for achieving various functional nanophotonic devices.The as–fabricated latex assembly can also act as prototype models in theory simulation fields for optical materials.

ASSOCIATED CONTENT

Supporting Information


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The morphological observations and wetting behaviors of FAS modified groove–wall–structured template (Figure S1), Adhesion force and the inserted water CA for different groove–structured template (Figure S2), more details of assembled template and substrate (Figure S3–S4), Lateral and top view of SEM images of more details linear colloidal assembled (Figure S5–S6), SEM images of linear and heterogeneous colloidal arrays with different morphology (Figure S7–S8) and SEM images of as–prepared colloidal crystal microrings (Figure S9). This material is available free of charge via the Internet at http://pubs.acs.org. Corresponding Author (Prof. Jingxia Wang) E–mail: [email protected] ACKNOWLEDGMENTS The authors thank the financial support by the National Nature Sciences Foundation (Grant Nos.51373183, 21421061, 91127029, and 21074139) and 973 program (Nos. 2013CB933000).

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Bottom-Up Strategy Using Superwettability for the

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