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“Capillary-Bridge Lithography” for Patterning Organic

Communication
Crystals toward Mode-Tunable Microlaser Arrays
Jiangang Feng, Xiangyu Jiang, Xiaoxu Yan, Yuchen Wu,* Bin Su, Hongbing Fu,*
Jiannian Yao, and Lei Jiang

Single-crystalline organic semiconductors possess chemically “gas–liquid–solid” triphase contact line, is often dominated by
tunable optoelectronic properties, high optical cross section, isotropic capillary force, inducing an uncontrollable pining or
low trap density, and remarkable mechanical flexibility, thereby centripetal dewetting of liquid.[17–19] Consequently, the molec-
bringing fundamental capabilities to light generation, propaga- ular packing and crystallization is disordered at the liquid
tion, amplification, detection, and modulation.[1–5] Compared rim, yielding organic crystals with broadly distributed grain
to the fabrication of inorganic micro-/nanostructures (such as sizes, random crystallographic orientation, and high defect
direct-bandgap III–V semiconductors) with complicated fabri- density.[20–23]
cation process, solution-processing patterning methods, have To enhance the crystal quality in solution patterning pro-
provided effective approaches for organic semiconductors to cess, regulating the crystallization position and capillary force
circumvent those limitations, which allows for low-cost and are required simultaneously, which can be realized by control-
wafer-scale integration of organic crystals.[6–9] Typical solu- ling surface chemical state and geometry. Aizenberg and co-
tion patterning methods, such as dip-pen lithography,[10,11] workers[24–26] employed patterned self-assembled monolayers
inkjet printing,[12,13] and soft lithography,[14–16] can fabricate (SAM) to tuning the surface chemical state of substrate. Using
micrometer- or nanometer-sized liquid droplet or film with patterned SAM with different functional groups, both inorganic
controlled position and geometries, which yields patterned and organic crystals with controlled nucleation sites, crystallo-
organic structures after evaporation of solvents. For example, graphic orientation and patterning has been fabricated. Surface
Kim et al. reported a micromolding in capillaries method, geometry also play important role on controlling the crystal-
which realized the confinement of precursor liquid by an elas- lization position and capillary force. In particular, Cavallini et
tomeric stamp and fabrication of polymer patterns.[16] In those al. developed a lithographically controlled wetting approach
conventional solution process, the drying front of liquid, i.e., to mediate the capillary force under the guidance of a micro-
structured stamp, thus leading to the patterning of organic
crystals.[27–29] However, it is still remain challenging to pre-
Dr. J. G. Feng, Dr. X. Y. Jiang, Dr. Y. C. Wu, cisely control geometry, grain size, position, and orientation of
Prof. L. Jiang
Key Laboratory of Bio-inspired Materials
organic single crystals.
and Interfacial Science Here, we report a high-efficiency method, termed capillary-
Technical Institute of Physics and Chemistry bridge lithography, which can afford to fabricate high-quality
Chinese Academy of Sciences organic single-crystal arrays. The receding of “gas–liquid–
Beijing 100190, P. R. China solid” triphase contact line in dewetting process is manipu-
E-mail: wuyuchen@[Link]
lated by a template with periodically arranged micropillars
Dr. X. X. Yan
State Key Joint Laboratory of Environment and asymmetric wettability, yielding individual capillary bridge
Simulation and Pollution Control arrays anchored onto the tops of micropillars. The location
School of Environment and geometry of capillary bridges are strictly regulated by the
Tsinghua University asymmetric-wettability micropillars, thus realizing the con-
Beijing 100084, P. R. China
finement of nucleation site and growth orientation of organic
Dr. B. Su
Department of Chemical Engineering
crystals. 1D single-crystalline organic structure arrays with high
Monash University crystallinity, tunable size and precise positioning can be fabri-
Clayton, Victoria 3800, Australia cated by the capillary-bridge lithography, yielding low-threshold
Prof. H. B. Fu, Prof. J. N. Yao Fabry–Pérot (FP) mode lasing. We also show that fabrication
Beijing National Laboratory for Molecular Science (BNLMS) of organic microring arrays can be realized by designing the
Key Laboratory of Photochemistry micropillars with corresponding geometry. High-performance
Institute of Chemistry
Chinese Academy of Sciences whispering-gallery-mode (WGM) lasing emission has been
Beijing 100190, P. R. China demonstrated on those microring optical resonators. Our tech-
E-mail: [Link]@[Link] nique provides a versatile approach to patterning organic crys-
Prof. L. Jiang tals with designable structure and tunable physical properties
School of Chemistry and Environment for optoelectronic applications.
Beihang University
Beijing 100191, P. R. China
Capillary bridge is a ubiquitous phenomenon observed
between two neighboring solid surfaces in nature, which
DOI: 10.1002/adma.201603652 dominates the wet granular pile,[30] liquid transport between

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shorebird beak,[31] and wet adhesion of beetles.[32] The mor- arranged micropillars and a flat substrate (Figure 1b), which
Communication

phology and transport dynamics of capillary bridge can be is consistent with the fluorescence microscopic observation
tailored through controlling the topography and chemistry of (Figure 1f). The rapture of continuous liquid film proceeds with
solid surface, thus bringing their implementation as a plat- the evaporation of organic solvents, which is dominated by the
form for manipulating capillary force. Recently, Aizenberg and capillary forces at micropillar surface. A sequential dewetting
co-workers demonstrated that capillary bridges can dominate process can be observed by the fluorescence microscopy and
the self organization of mesoscale pillars into ordered, hier- simulated by CFD. The receding of triphase contact line first
archical helical assemblies.[33–35] To employ capillary bridges happens at the gaps between two columns of micropillars due
for patterning organic crystals, two conditions must be met: to the lower liquid–solid contact area (Figure 1c,g). With the
(i) isolated microscaled capillary bridges with regulated geom- proceeding of liquid dewetting, the organic liquid is separated
etry, size and position can be fabricated, which enables the into individual rows (Figure 1d,h). Finally, isolated capillary
patterning of organic structure. (ii) The dewetting process of bridges are generated and anchored onto the micropillars’ tops
capillary bridge needs to be regulated, which benefits crystal- (Figure 1e,i). Further evaporation of organic solvents in capil-
linity and ordered molecular packing of organic crystals. lary bridges will induce the receding of triphase contact line
To control patterning and dewetting dynamics of capillary (see the side view snapshots of simulated dewetting process in
bridges, we fabricated an asymmetric-wettability surface on a Figure S4, Supporting Information). When the concentration of
micropillar-structured template (Figure S1, Supporting Informa- TDSB molecules is saturated, nucleation and growth of organic
tion). On each single micropillar, asymmetric wettability refers crystals happens in each individual capillary bridge. Different
to the lyophilic top and lyophobic sidewall, which can be real- from the microdroplet generated by the inkjet printing, soft
ized by a selective modification of low-surface-energy heptade- lithography, and nanoimprinting, the capillary bridges possess
cafluorodecyltrimethoxysilane (FAS) molecules onto sidewalls predefined geometry, precisely regulated position and highly
of micropillars. In selective modification process, a protection controllable dewetting dynamics. Owing to the highly design-
layer was covered onto the tops of micropillars followed by FAS able and controllable characteristics of capillary-bridge lithog-
modification and remove of protection layers (detailed sche- raphy methods, 1D organic single crystals with homogeneous
matic illustration and description can be found in Figure S2, size, strict alignment, and precise position have been fabricated
Supporting Information). To validate the successful fabrication and shown a green fluorescence emission (Figure 1j,k). The
of asymmetric-wettability micropillar-structured templates, the atomic force microscopy (AFM) topography and height diagram
spatial distribution of FAS molecules was characterized by the illustrate flat surface and smooth boundary of as-formed 1D
Raman mapping. As shown in Figure S3 of the Supporting crystal, which indicates the high-crystallinity nature (Figure 1i).
Information, high intensity FAS signals can be detected on the A quasi-square-shaped cross section with height of ≈0.5 µm
gap regions of micropillar-structured template, whereas nearly and width of ≈0.5 µm has been observed (Figure 1i).
no FAS signal emerges on the top regions, indicating the suc- The asymmetric wettability of micropillars is indispensable
cess of our selective modification. To evaluate the asymmetric for the successful fabrication of 1D crystal arrays in capillary-
wettability property, contact angle (CA) of tops and sidewalls bridge lithography process. To confirm this, we performed
of micropillars was measured. Low CA of 18.9° ± 1.6° can capillary-bridge lithography experiments on micropillar-struc-
be observed at the top regions, whereas the FAS-modified tured template with symmetric wettability. On the micropil-
sidewall regions show a high contact angle of 103.2° ± 3.7° lars without FAS modification, top and sidewall regions show
(Figure S3b,c, Supporting Information). The lyophobic char- contact angles of 18.9° ± 1.6° and 5.7° ± 0.8°, indicating a sym-
acteristic of sidewall can prevent the wetting of sidewalls and metric lyophilic characteristic (Figure S5, Supporting Informa-
suspend the liquid onto the tops of micropillars. tion). In this scenario, the gaps between micropillars can be
To fabricate organic crystals, a lasing compound, filled by organic liquid, generating an unbroken liquid film
1,4-dimethoxy-2,5-di[4-(methylthio)styryl]benzene (TDSB) was and disordered organic structures. Furthermore, micropillar-
employed due to its H-aggregated cofacial molecular packing structured template was modified with FAS molecules on both
with high material gain and low lasing threshold.[36] An organic sidewalls and tops, yielding a symmetric lyophobic surface
liquid thin film was sandwiched between the target flat sub- (Figure S6, Supporting Information). As a result, the organic
strate and asymmetric-wettability micropillar-structured tem- crystals turn irregular in shape and uncontrollable in size,
plate (Figure 1a). With the evaporation of organic solvents, the which may be caused by low adhesion of lyophobic tops. The
rapture of liquid film happens, generating isolated microscaled wettability of substrates plays important role on the successful
capillary bridges anchored onto micropillars. The geometry, growth of crystals. Typical substrates, such as glass, silicon
size, and position of capillary bridges are determined by the and ITO, are lyophilic, which allows the successful patterning
micropillars, thus enabling the patterning of organic structures. of organic crystals (Figure S7, Supporting Information). For a
After the further dewetting of capillary bridges, the organic- highly lyophobic substrate, the dewetting process is difficult to
semiconductor molecules achieve supersaturation and crystal- be controlled, thus leading to the disordered growth of organic
lization happens at the triphase contact line. crystals. Concentration of organic semiconductor is also influ-
To gain further insights into the mechanism of capillary- ence the yield of organic structures. Too low or high concen-
bridge lithography method, we carried out computational tration will induce the lower formation ratio of organic crystal
fluid dynamics (CFD) simulations and in situ fluorescence arrays (Figure S8, Supporting Information). Meanwhile, the
microscopy characterization. The CFD simulations start with width of 1D crystals can also be controlled by changing the con-
constructing liquid film sandwiched between a periodically centration (Figure S9, Supporting Information). The width of

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Figure 1. Fabrication and characterization of 1D organic single-crystal arrays. a) Schematic illustration of the capillary-bridge lithography technique for
fabrication of 1D organic single-crystal arrays. A liquid thin film was firstly confined between an asymmetric-wettability micropillar-structured template
and a flat target substrate followed by dewetting and formation of isolated capillary bridges anchored onto micropillars, which finally generates 1D
organic crystals onto target substrate. b–e) Computational fluid dynamics (CFD) simulation of dewetting and capillary-bridge formation of organic
liquid during evaporation process of organic solvents. f–i) In situ fluorescence microscopic observation of dewetting process during the capillary-bridge
lithography process. The dewetting process and rapture of organic liquid film can be guided by capillary forces, which generate controllable concave
liquid menisci and ordered liquid shrinkage process. Both experiments and simulations can demonstrate that micropillars with asymmetric wettability
can manipulate the capillary bridges. j) Fluorescence image and k) SEM image of 1D organic crystal array fabricated on flat substrate. l) AFM topog-
raphy and height diagram of a single organic 1D crystal, illustrating a cross section of ≈0.5 × 0.5 µm.

TDSB crystals can be tuned from ≈0.12 to 0.82 µm when the (Figure 2f). To further evaluate the crystallinity, morphology, and
concentrations vary from 0.1 to 2.0 mg mL−1. growth direction of TDSB crystal, transmission electron micros-
A low-magnification fluorescence microscopy (Figure 2a) copy (TEM) combined with selected-area electron diffraction
demonstrates that large-area organic crystal arrays with (SAED) were performed on a single 1D crystal. 1D structure
homogeneous size and precise position was fabricated by cap- with straight boundary can be observed from the TEM image
illary-bridge lithography. Further cross-polarized fluorescence (Figure 2g). SAED pattern obtained from this 1D crystal presents
microscopy displays dark-field image of 1D organic crystals sharp diffraction spots, indicating its high-crystallinity nature
under different polarization angle (Figure 2b,c). With the 45° (Figure 2g, inset). Single-crystal structure of TDSB (CCDC No.
rotation of polarization angle, all 1D crystals extinguish cross- 675387) shows a monoclinic structure with a = 8.15 Å, b = 5.42 Å,
polarized fluorescence simultaneously (Figure 2c). The angle- c = 26.14 Å, α =γ = 90°, β = 97.37° and space group of P21/c.[37]
dependent fluorescence intensity demonstrates the ordered According to this structure, zone axes of [010] and [001] are
crystallographic alignment of these single crystals (Figure 2d,e). determined as parallel and perpendicular to the long axis of
Scanning electron microscopy (SEM) image of a single TDSB 1D structure from the SAED pattern. By simulating the growth
crystal illustrates the smooth surface and flat end face of crystals morphology of TDSB crystal based on the crystal structure,

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Figure 2. Controllable dewetting and crystallization process by capillary-bridge lithography technique. a) Low-magnification fluorescent image presents
large-scale 1D organic arrays with strict alignment and precise position. b,c) Cross-polarized fluorescence image of 1D organic single-crystal arrays.
d) PL spectra at highest and lowest intensity under different polarized angle. e) Angle-dependent PL intensity of 1D organic arrays. Simultaneous varia-
tion of fluorescent intensity indicates the uniform crystallographic orientation of 1D crystal arrays. f) SEM, g) TEM images of 1D organic single crystal.
Inset shows a SAED pattern recorded from the region shown in (g). h) Theoretical predicted growth morphology shows 1D growth of TDSB crystal
along the [010] direction. i) GIWAXS pattern of TDSB crystals, illustrating a preferential growth of crystal arrays along [010] crystallographic orientation.
The (hk) indexes of the (20) and (01) are shown.

we find that the crystal tends to grow along the [010] direction the one single 1D organic crystal. Figure 3a presents a sche-
and form a 1D architecture (Figure 2h). To further quantify the matic of organic crystal on silica substrate, which is pumped by
crystallographic alignment of 1D crystal arrays in wafer scale, a pulsed laser. Room temperature lasing oscillator was achieved
we further performed a grazing incidence wide-angle X-ray scat- in the individual 1D organic crystal by increasing the pump
tering (GIWAXS) with the X-ray direction along the long axis fluence of the optical excitation. Figure 3b shows the emis-
of 1D arrays. The (hk) indexes of the (20) and (01) are shown sion spectra at different pump fluence near threshold obtained
in Figure 2i. Note that a sharp spots with in-plane momentum from one sample 1D crystals with cavity length L = 20.0 µm.
transfer vectors (Qxy) of 1.1 Å−1 and out-of-plane momentum The 1D organic crystal exhibits a broad peak centered at 500 nm
transfer vectors (Qz) of 0.15 Å−1 were observed, which can be with a full-width at half-maximum (FWHM) of 25 nm at low
assigned to (010) plane according to the crystal parameters. pump fluence of 75 nJ cm−2. This broad peak can be assigned
The results indicate that [010] axis is nearly parallel to the film to the spontaneous emission of TDSB, which is consistent with
of substrate with highly uniform orientation. Combining with the PL spectrum of TDSB crystal shown in Figure S10 of the
SAED results, we can conclude that crystal arrays are preferen- Supporting Information. With improving input power, a set of
tially oriented along [010] crystallographic orientation. narrow peaks around 500 nm increase sharply in intensity. The
In order to investigate optical microcavity effect and lasing log-log scale plot of integrated peak intensity versus pump flu-
emission of these 1D organic crystals, a beam of 400 nm pulsed ence shows an “S”-shaped profile, indicating the transition from
laser with beam waist of 30 µm was used to uniformly excite spontaneous emission via amplified spontaneous emission

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Figure 3. Lasing performance of assembled 1D single-crystalline structures. a) Schematic illustration of 1D organic laser lying on a SiO2 substrate. A
400 nm pulsed laser source pumps a single crystal and the laser emits with wavelength around 500 nm. b) μ-PL spectra of nanowires under a set of
pump fluence. Inset shows double logarithmic curve of an organic laser with a low threshold of 410 nJ cm−2 (left) and time resolved photoluminescence
at different pump fluence (right). The S-shaped curve presents from spontaneous emission via amplified spontaneous emission to full lasing emission.
c) μ-PL spectra collected from the TDSB Fabry–Pérot cavity with length of 10, 15, and 20 µm. d) μ-PL image of TDSB wires of different length above
lasing threshold, showing a clear lasing characteristic of Fabry–Pérot cavity with two-tip emission. e) Simulation of absolute electric field distribution of
nanowires with different length, confirming the Fabry–Pérot lasing mode in 1D cavities. f) Mode spacing of lasing peaks versus 1/L of TDSB 1D lasers.

to full lasing emission with the increasing input energy To further tune the lasing mode, we fabricated 1D crystals
(Figure 3b, left inset). The lasing threshold can be determined of different lengths by changing length of micropillars and
as 410 nJ cm−2 from the “S”-shaped curve. Above the lasing recorded their μ-PL spectra above lasing threshold. Figure 3c
threshold, the μ-PL image presents two strong green impres- shows PL spectra of 1D crystals with lengths of 10, 15, and
sive spots at the two ends of 1D crystal (Figure S11a, Supporting 20 µm. Different numbers of resonance modes can be sup-
Information), which illustrates a strong axial waveguiding ported on 1D cavity with varied lengths. The strong light emis-
behavior and typical a FP lasing emission. Above the threshold, sion at two ends of 1D crystals indicates generation of FP lasing
two end facets serve as reflector mirror to back and forth propa- on these crystals with different lengths (Figure 3d). Finite-dif-
gate light, leading to the establishment of resonance and lasing ference time-domain (FDTD) method was employed to simulate
emission. To evaluate uniformity of lasing performance on dif- the optical resonance mode supported in these 1D cavities. The
ferent 1D single crystals, we measured lasing thresholds of 50 simulated 2D electric field distribution along the cross section
different 1D structures on a single substrate (Figure S11b, Sup- of 1D crystal confirms that the FP-mode indeed exists along the
porting Information). The narrowly distributed lasing threshold length direction of the individual crystals with different lengths
might indicate the highly homogeneous morphology, molecular (Figure 3e). To further confirm this FP-mode of microwires
packing and geometry of these organic crystals. To confirm the laser microresonators, 9 microwires with different lengths were
temporal coherence of lasing emission, we carried out time studied. For the PL spectra of FP-type resonance, the mode
resolved photoluminescence. The spontaneous emission life- spacing Δλm (between two adjacent resonance peaks) is given by
time was as long as 1.43 ± 0.03 ns at low excitation density
(75 nJ cm−2). Faster PL decay happens with the increasing exci-
λ2
tation density and PL lifetime decrease to <25 ps at the excita- ∆λ = (1)
tion above lasing threshold (Figure 3b, right inset). 2L × n − λ ( dn /dλ ) 

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where L is the length of microwire (2L: the round trip length homogeneous diameter of 8 µm and line width of ≈0.5 µm.
Communication

within one microwire microresonator), λ is the wavelength of The spacing and position of microrings is strictly regulated by
light, n is the phase refractive index, and dn/dλ is the disper- the arrangement of micropillar-structured template. Both fluo-
sion relation. A plot of 1/L of the wires versus the mode spacing rescence image and SEM image show a single microring with
Δλm at 500 nm is shown in Figure 3f. The best-fit line (black smooth surface and boundary (Figure 4b,c). TEM image pre-
line) is clearly linear, which confirms that the wires operate sents a part of microring with homogeneous width and smooth
as FP-mode resonator along the length rather than the other boundary along the microring (Figure 4d). SAED pattern col-
dimensions of the wires. As demonstrated above, the organic lected at this region shows disordered diffraction spots, indi-
1D single-crystal array provides both a gain medium and a FP- cating low crystallinity of microrings (Figure 4c, inset), which
mode resonator for lasing. might attribute to continuous changing of molecular packing
By tuning the geometry of micropillars, we could assemble orientation. However, no obvious crack can be observed, which
the molecules into different morphologies for fabricating enables the confinement of light and lasing emission from
microcavities with different resonance modes and tunable these organic microrings. Further AFM characterization shows
lasing emission. To achieve the whispering-gallery-mode a smooth tops surface and homogenous width of microring
lasing, we employed a ring-shaped micropillar-structured tem- (Figure 4e). The height of microring is determined as ≈0.5 µm.
plate (Figure S12, Supporting Information). After the guided To investigate the lasing emission in these microring resona-
dewetting process by micropillars, microring arrays of TDSB tors, pulsed pump laser was harnessed to uniformly excite one
were generated on target substrate. The dark-field fluores- single microring. At low pump fluence of 60 nJ cm−2, broad
cence image shown in Figure 4a displays microring arrays with spontaneous emission dominates the PL spectrum. Following

Figure 4. Fabrication and lasing emission of TDSB microring. Dark-field fluorescence image of a) TDSB microring arrays and b) a single microring.
c) SEM image presents a single microring with smooth boundary and flat surface. d) TEM image illustrates a segment of a microring, showing an
arc with homogeneous width. Inset is the corresponding SAED pattern, indicating that molecules stack into low-ordering state in microring. e) AFM
image and height diagram of microring. f) Power-dependent PL spectra of 8 µm diameter microring. Inset is integrated PL intensity as a function of
pump density of microring laser with diameter of 8 µm, showing lasing threshold around 310 nJ cm−2. g) Lasing spectra collected from the microring
cavities with diameters of 8, 12, and 16 µm. Inset shows the simulated resonance modes in microrings with different diameters. Whispering gallery
mode resonance can be established in these microcavities.

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the increase of the input power, strong lasing emission between two surfaces. This capillary-bridge lithography system was

Communication
peaks emerge and rise rapidly with the increased pump flu- kept at temperature of 60 °C for 12 h to evaporate DMF solvents. After
ence (Figure 4f). According to the integrated PL intensity the evaporation of organic solvents, the organic crystal patterns were
obtained after detachment of flat substrate and micropillar-structured
as a function of pump influence with log–log scale, we can template. To fabricate 1D organic single crystals with different length,
find an S-shaped curve with pronounced lasing threshold of we designed templates with different-length micropillars. The organic
310 nJ cm−2, which is lower than FP laser (Figure 4f, inset). microrings were assembled by harnessing the ring-shaped micropillars
The size of microring can be designed by tailoring the diameter with different sizes and the other conditions were kept same as
of ring-shaped micropillars. Here, three typical microrings with fabrication of 1D crystals.
diameters of 8.0, 12.0, and 16.0 µm were successively fabricated Fluidic Dynamic Simulation of Dewetting Process: The dewetting
process in capillary-bridge lithography system was modeled using the
and lasing spectra of those is shown in Figure 4g. The number
technology of CFD, which uses numerical methods to solve problems
of resonance mode can be tuned by controlling the diameter that involve fluid flows. The basic principle of this technology is to
of microrings. As mentioned above, the microwires act as the discretize the continuous fluid using proper algorithms, generating a
FP-mode cavity for light amplification. When two tails of the mesh as the computational domain. With specific boundary definition
wires joint together to form the microring, the light takes total and initial values, the overall flow filed information could be derived
internal reflection along the WGM path. Insets of Figure 4g by the literation solution of the governing equations on each mesh
element.[38,39] Detailed calculation methods is provided in Note S1 of the
illustrate the simulated electromagnetic field distribution of
Supporting Information.
microrings with diameter of 8, 12, and 16 µm, which demon- Characterizations: The morphological characteristics of micropillar
strates the excellent light-confinement in the WGM ring reso- structure templates, prepared organic crystals were investigated via
nator. Therefore, our fabrication method enables us to provide field-emission scanning electron microscopy (FESEM, Hitachi, S-4800,
highly uniform microrings array to realize WGM microlaser. Japan) at an accelerating voltage of 5.0 kV. A cross-polarized optical
In conclusion, high-quality organic 1D single crystal and microscope (Vision Engineering Co., UK) integrated with a charge-
microring arrays have been fabricated by capillary-bridge coupled device (CCD) camera was employed to record the optical and
fluorescent images of organic crystals and organic liquid film. To carry
lithography method. The continuous organic liquid film can be out the in situ observation of dewetting process, a capillary-bridge
divided into individual capillary bridges that identify the posi- lithography system was placed under a dark-field fluorescent microscopy
tion, size and growth orientation of organic structures. High- (Vision Engineering Co., UK) and the images was captured at different
performance FP and WGM lasing emission has been realized time. Raman mapping characterizations were carried out on DXR
on the 1D structures and microrings, respectively. Through Raman microscope (Thermal Fisher Scientific Inc., USA). Fluorescence
designing the size of micropillar-structured templates, organic spectra were recorded using an F-4500 fluorescence spectrophotometer
(Hitachi, Japan). Static contact angles (CAs) between micropillar
microcavities with different sizes can be tailored, yielding
surfaces and DMF were measured on a Dataphysics OCA20 contact-
mode-tunable lasing emission. These results identify a versa- angle system at ambient temperature. The AFM topography and
tile and efficient approach to bottom-up assembly of organic height diagram were collected on a Bruker MultiMode 8 Atomic Force
molecules into microstructure patterns with designable geom- Microscope. TEM images and SAED of organic structures were recorded
etry, size, alignment, and position, allowing for integration of by a JEOL TEM-2100 operating at a 200 kV accelerating voltage to
organic microlasers with tunable lasing emission. More gen- evaluate the morphology and crystallinity. The growth morphology and
molecular stacking is calculated based on the crystal structure using
erally, this capillary-bridge lithography method shows clearly
Materials Studio package.[40] To quantify the crystallographic alignment
possibility of assembling nanoscaled building blocks, including of 1D organic crystals, grazing-incidence wide-angle X-ray scattering
organic small molecules, polymers and inorganic nanocrystals, (GIWAXS) was performed on XEUSS SAXS/WAXS system with incidence
into functional micro-/nanostructure arrays toward property- angle of 0.2°.
by-design fabrication of electronic, photonic, and biomedical Lasing Characterization and Numerical Calculation: To obtain the lasing
devices. emission properties of organic 1D crystals and microrings, a mode-locked
Ti:sapphire laser (λpump = 400 nm) with 150 fs pump pulses were focused
on an individual organic structure under a home-made microscope
equipped with a 50 × 0.9 numerical aperture (NA) objective. The laser beam
size was focused with an optimized beam waist of 30 µm to uniformly
Experimental Section excite the selected organic structures in a 2D movable table. The excited
Patterning Organic Crystals by Capillary-Bridge Lithography: The PL was coupled to an optical fiber (diameter 25/125 µm for core/cladding)
micropillar-structured substrate was fabricated by photolithography and collected through a liquid-nitrogen-cooled CCD (SPEC-10-400B/LbN,
followed by chemical etching. The geometry, size and arrangement of Roper Scientific). The resonance modes of FP and WGM microcavities
silicon micropillars can be regulated by designing the photomask and were calculated by FDTD method through constructing TDSB structures
controlling the etching process (detailed processing method is provided (refractive index, nTDSB = 1.8) on a quartz plate (nquartz = 1.3). For 1D cavity,
in Supporting Information). The asymmetric wettability of micropillars a cross section of 0.5 × 0.5 µm was constructed and the cavity lengths
was constructed by FAS-molecule selective modification. Detailed were set as 10, 15, and 20 µm, which is consistent with the length of 1D
modification process is given in the Supporting Information and crystals in experiment. The optical resonance modes of microrings were
illustrated in Figure S1 of the Supporting Information. To manipulate the simulated on ring-shaped microcavities with 0.5 µm height and width.
growth and patterning of organic single crystals, line-shaped micropillars The diameters of organic microrings were varied (8, 12, and 16 µm) to
with length of 10 µm, width of 1 µm, row spacing of 5 µm, column evaluate the impacts of cavity size.
spacing of 2 µm and height of 15 µm was first employed to fabricate
1D single-crystal arrays. At the beginning of capillary-bridge lithography
process, a droplet of TDSB dissolved in N,N-dimethylformamide (DMF) Supporting Information
was carefully loaded on the surface of micropillar-structured asymmetric-
wettability template followed by covering a flat target substrate (here Supporting Information is available from the Wiley Online Library or
was a silica slide), thus yielding an organic-liquid thin film sandwiched from the author.

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DOI: 10.1002/adma.201603652