1

3
Analyzing nanostructures in mesogenic hostguest systems
4
for polarized phosphorescence
5
6
7 Yu-Tang Tsai
a
Q1 , Chien-Yu Chen
a
, Li-Yin Chen
a
, Su-Hao Liu
a
, Chung-Chih Wu
a,
, Yun Chi
b
,
8 Shaw H. Chen
c
, Hsiu-Fu Hsu
d
, Jey-Jau Lee
e
9
a
Department of Electrical Engineering, Graduate Institute of Electronics Engineering, Graduate Institute of Photonics and Optoelectronics, and Innovative
10 Photonics Advanced Research Center (i-PARC), National Taiwan University, Taipei 10617, Taiwan, ROC
11
b
Chemistry Department, National Tsing-Hua University, Hsin-Chu 30013, Taiwan, ROC
12
c
Chemical Engineering Department, University of Rochester, Rochester, NY 14623-1212, USA
13
d
Chemistry Department, Tamkang University, Taipei 25137, Taiwan, ROC
14
e
National Synchrotron Radiation Research Center, Hsin-Chu 30076, Taiwan, ROC
15
16
17
1 9
a r t i c l e i n f o
20 Article history:
21 Received 20 October 2013
22 Received in revised form 5 November 2013
23 Accepted 12 November 2013
24 Available online xxxx
25 Keywords:
26 OLEDs
27 Phosphorescence
28 Polarized emission
29 Liquid crystal
30 GIXS
31
3 2
a b s t r a c t
33 Feasibility of polarized phosphorescent organic light-emitting devices (OLEDs) had been
34 previously demonstrated by combining a discotic Pt(II) complex with a glassy-nematic
35 oligouorene host to form a mesogenic hostguest phosphorescent emitting system. Pre-
36 vious photophysical studies suggested that in the hostguest lm, the Pt(II) complex
37 tended to aggregate into columnar stacks, exhibiting metalmetal-to-ligand charge trans-
38 fer (MMLCT) emission. Both host molecules and guest aggregates in the hostguest lms
39 could be oriented by a conductive alignment layer, giving rise to polarized phosphores-
40 cence from the Pt(II) aggregates. Nevertheless, lm morphologies and nanostructures of
41 the mesogenic hostguest systems have remained to be elucidated. In this work, grazing
42 incidence X-ray scattering (GIXS) was carried out to analyze nanostructures in both neat
43 lms of the discotic Pt(II) complex and mesogenic hostguest mixture lms. In addition,
44 confocal laser scanning microscopy (CLSM) was also utilized for visualization of the mor-
45 phologies of mesogenic hostguest systems. The columnar axes of nanostructured Pt(II)
46 stacks lying on the alignment-treated surfaces were found to be preferentially oriented
47 perpendicular to the rubbing direction, which is responsible for the observed linearly
48 polarized phosphorescence.
49 2013 Published by Elsevier B.V.
50
51
52 1. Introduction
53 The ability to organize nanostructures in ordered
54 orientations over large areas is of primary importance for
55 the bottom-up fabrication of nanostructure-based devices.
56 By controlling the spatial arrangement and the degree of
57 ordered nanostructures, it is possible to control polariza-
58 tion of light for optical information processing, such as
59 displays, optical communication, optical storage, and ste-
60 reoscopic (3D) imaging systems etc. [1,2]. For instance,
61 polarized electroluminescence devices would be useful
62 for backlights of liquidcrystal displays (LCDs) to make
63 them more power efcient and for pixels of 3D displays
64 to simplify their congurations [35]. As such, there have
65 been substantial efforts in developing polarized organic
66 light-emitting devices (OLEDs) [619]. With the strong
67 intrinsic anisotropy in polymer chains, conjugated
68 polymers that can form well aligned thin lms [13
69 18,20], such as mesogenic polyuorenes [2124], repre-
70 sent a common class of active materials for polarized
71 OLEDs. Meanwhile, with better control of molecular struc-
72 tures and material purity, mesogenic conjugated oligomers
73 that can form well aligned lms are another promising
1566-1199/$ - see front matter 2013 Published by Elsevier B.V.
http://dx.doi.org/10.1016/j.orgel.2013.11.025

Correspondin Q2 g author. Tel.: +886 2 33663636.

E-mail address: chungwu@cc.ee.ntu.edu.tw (C.-C. Wu).
Organic Electronics xxx (2013) xxxxxx
Contents lists available at ScienceDirect
Organic Electronics
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74 class of active materials for polarized OLEDs [612]. Li-
75 quidcrystalline (LC) oligouorenes have been reported
76 as hosts to guide molecular orientation of guest emitters,
77 forming hostguest emitting systems for highly polarized
78 and efcient OLEDs spanning the whole visible spectrum
79 and white-light emission [811].
80 Most of previous efforts in polarized OLEDs, however,
81 were mainly focused on uorescence mechanisms. Yet,
82 the development of OLEDs in recent years has largely
83 shifted toward phosphorescent OLEDs [25,26], since phos-
84 phorescent OLEDs could effectively utilize both singlet and
85 triplet excitons and realize essentially 100% internal quan-
86 tum efciencies [27,28]. As such, it is of both scientic and
87 technical importance to explore the possibility of achieving
88 polarized phosphorescent OLEDs. In a recent publication
89 [29], we have reported an initial attempt to realize work-
90 able and functional polarized phosphorescent OLEDs by
91 mixing a discotic mesogenic phosphorescent metal (Pt(II))
92 complex N200 (Fig. 1) with a glassy-nematic oligouorene
93 host (F(MB)5, Fig. 1) to form the corresponding mesogenic
94 hostguest (phosphorescent) emitting system.
95 Spectral properties of the neat N200 spin-cast lms sug-
96 gest N200 molecules exhibit strong ground-state intermo-
97 lecular interactions (instead of simply excited-state
98 interaction, like excimers) and they tend to self-assemble
99 to form aggregates in lms [29]. Previous luminescence
100 characterization of bulk samples of these Pt(II) complexes
101 revealed that they exhibited red emission only in the
102 columnar mesophase, while monomer-like green emission
103 was observed in isotropic liquid state or dilute solution
104 [30]. Thus the appearance of red emission in N200 samples
105 is a good indication of columnar-like mesophase packing.
106 Due to the columnar mesomorphic nature of N200 and
107 the resemblance of photophysical properties in spin-cast
108 lms to those of bulk samples in the liquid crystal phase
109 [30], presumably the square-planar N200 molecules also
110 pack into a one-dimensional columnar stacking arrange-
111 ment in spin-cast lms.
112 To account for the observed mesomorphism, photo-
113 physical characteristics, and polarized transitions of these
114 materials in various states and compositions, we proposed
115 that N200 self-assemble into columnar stacking in the
116 hostguest lm, exhibiting metalmetal-to-ligand charge
117 transfer (MMLCT) emission of the Pt(II) complex N200
118 [29,30]. Both the host molecules and guest aggregates in
119 the hostguest lms were successfully aligned on the
120 rubbed conducting polymer alignment layer. With such
121 alignment and effective host-to-guest energy transfer,
122 polarized red phosphorescence and electrophosphores-
123 cence from the phosphorescent Pt(II) complex as aggre-
124 gates were observed. Although this proposed scenario
125 appeared consistent with all the physical and photophysi-
126 cal characterizations reported earlier, experimental
127 observations are desired for lm morphologies and nano-
128 structures of the N200-oligouorene hostguest systems.
129 In this work, the grazing incidence X-ray scattering (GIXS)
130 was performed to investigate morphologies and nano-
131 structures in both neat N200 and its mixture with
132 F(MB)5 lms. In addition, the confocal laser scanning
133 microscopy (CLSM) was also utilized for the visualization
134 of morphologies of mesogenic hostguest systems.
135 2. Experiment
136 2.1. Materials
137 Fig. 1 shows the mesogenic materials, the Pt(II) complex
138 N200 and the uorene oligomer F(MB)5 used in this work.
139 N200 is a Pt(N^N)
2
complex, in which N^N = 2-(3-(3,4,5-
140 trihexoxyphenyl)-1H-pyrazol-5-yl) pyridine. It adopts the
141 distinctive pyridyl azolate as ligands, which are known to
142 form strong chelate bonding with Pt ions and render the
143 molecule a square-plannar geometry, affording distinctive
144 emission (phosphorescent) properties [3032]. Indeed,
145 such Pt(II) complexes exhibit rather efcient green phos-
146 phorescence at room temperature in dilute solutions [30].
147 Further attaching alkyloxyphenyl groups with the alkyl
148 chain (i.e., 3,4,5-trihexoxyphenyl) onto the ligands imparts
149 certain exibility to the molecular core and mesomorphic
150 characteristics, thereby yielding luminescent metallomes-
151 ogens [30,3336]. As studied by polarizing optical micros-
152 copy and differential scanning calorimetry, N200 shows
153 liquidcrystalline properties across a wide temperature
154 range. Upon heating the crystalline samples of these Pt(II)
155 complexes, a transition from the solid to the columnar
156 mesophase (as veried by X-ray diffraction [30]) and a
157 transition from the mesophase to the isotropic liquid
158 occurs at 98 C and 342 C, respectively. The details of
159 syntheses and basic material properties of the Pt(II) com-
160 plexes had been reported elsewhere [30].
161 Employed as the host, the uorene oligomer F(MB)5
162 consists of ve uorene units on the backbone and two
163 2-methylbutyl substituents at C9 atoms [8,9]. F(MB)5
164 belongs to a class of glass-forming nematic oligouorenes,
165 that is, materials that exhibit the nematic mesophase at
166 elevated temperatures and yet also the stable glass phase
167 at room temperature [811]. As studied by polarizing opti-
168 cal microscopy and differential scanning calorimetry,
Fig. 1. The mesogenic materials, the Pt(II) complex N200 and the uorene
oligomer F(MB)5, used in this work.
2 Y.-T. Tsai et al. / Organic Electronics xxx (2013) xxxxxx
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169 F(MB)5 exhibits a glass transition (T
g
) at 89 C and a
170 nematic-to-isotropic transition at 167 C. It had been dem-
171 onstrated that liquidcrystal glass of F(MB)5 could be
172 formed by freezing its mesophase down to room tempera-
173 ture without crystallization, and that the aligned glassy
174 nematic lm of F(MB)5 could be formed by utilizing meso-
175 phase-mediated alignment (e.g., assisted by the rubbed
176 alignment layer of a polyimide or a conducting polymer)
177 at elevated temperatures [8,9]. F(MB)5 is also an efcient
178 uorescent blue emitter on its own with a thin-lm quan-
179 tum yield of >50% [8,9]. Detailed syntheses and character-
180 izations of F(MB)5 could be found in previous publications
181 [8].
182 2.2. Molecular Alignment
183 To conduct and study molecular alignment of the
184 mesogenic oligouorene/mesogenic Pt(II) complex host
185 guest mixtures, different sample structures and alignment
186 approaches were tested. In scheme I, the active thin lms
187 under investigation were spin-coated onto the quartz or
188 Si/SiO
2
substrates and then uniaxially rubbed with a cloth
189 for surface alignment. In scheme II, a conducting polymer,
190 poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate)
191 (PEDOT:PSS), was used as the alignment layer. PEDOT:PSS
192 was spin-coated onto quartz or Si/SiO
2
substrates, dried at
193 130 C in air, and uniaxially rubbed with the cloth. The ac-
194 tive thin lms under investigation were then spin-coated
195 onto the rubbed PEDOT:PSS for surface alignment. In both
196 schemes I and II, the active layer to be aligned could be a
197 neat lm of F(MB)5, a neat lm of the Pt(II) complex
198 N200, or a hostguest mixture lm of F(MB)5 and Pt(II)
199 complex N200 (with 25 wt.% of N200). To induce meso-
200 phase-mediated molecular alignment, all samples were
201 further annealed at elevated temperatures for 1 h: 150 C
202 for neatN200 lms and 120 C for the neat F(MB)5 or the
203 F(MB)5:N200 mixture lms. With an aim to construct
204 polarized phosphorescent OLEDs using the mesogenic
205 Pt(II) complexes, we rst tried to use the rubbed PED-
206 OT:PSS lm to align all material layers (i.e., scheme II),
207 since PEDOT:PSS was to be used as the conductive align-
208 ment layer in polarized OLED. However, since scheme II
209 (the one preferred for device applications) failed to orient
210 the neat Pt(II) complex lms, scheme I was followed to
211 investigate fundamental properties of neat Pt(II) complex
212 lms [29]. Scheme II was successfully implemented to
213 accomplish orientation in neat F(MB)5 and the
214 F(MB)5:N200 mixture lms for both fundamental studies
215 and device applications.
216 2.3. Grazing incidence X-ray scattering
217 GIXS was conducted for the analysis of hostguest
218 systems. Compared to other conventional techniques for
219 morphological characterizations (e.g. atomic force micros-
220 copy, scanning or transmission electron microscopy etc.),
221 GIXS has the particular advantage of being able to provide
222 structural/morphological information of a thin lm at dif-
223 ferent scales [3744], instead of being limited to local
224 observation. Fig. 2 illustrates the conguration of the GIXS
225 measurement, which was conducted at the BL17A end sta-
226 tion of the National Synchrotron Radiation Research
227 Center, Hsinchu, Taiwan. The 9.3-keV (k = 1.33 ) beam
228 having a 1 mm beam diameter was directed at a 0.1 inci-
229 dence angle (h
IN
). The 2D scattering images were collected
230 by a MAR345 CCD detector array 210 mm away. To avoid
231 the reection of the incident beam from the substrate that
232 was strong relative to the scattering signals, aluminum
233 foils were applied as the semitransparent beam stop. The
234 thin-lm samples were kept at room temperature in air
235 during irradiation and GIXS image collection. In Fig. 2, h
IN
236 denotes the incident angle, and 2h is the diffraction angle
237 (relative to the sample-detector axis). The propagation
238 direction of the incident X-ray is dened as the Y axis,
239 the out-of-plane (OOP) direction relative to the sample
240 surface as the Z axis, and in-plane (IP) direction perpendic-
241 ular to the Y axis as the X axis. Q
X
and Q
Z
are the compo-
242 nents of the scattering vector Q along the IP (X axis)
243 direction and the OOP (Z axis) direction, respectively,
244 where Q = 4psin(h)/k and k = the X-ray wavelength. For
245 samples subjected to rubbing and annealing treatments
246 and thus having anisotropic in-plane characteristics, GIXS
247 was conducted in two different congurations. In the rst
248 conguration, the propagation direction of the incident
249 X-ray was parallel to the rubbing direction (i.e., the angle
250 between these two directions x= 0). In the second cong-
251 uration, the rubbing direction was rotated away from the
252 propagation direction of the incident X-ray by 90 (i.e.,
253 the angle between these two directions x= 90), thus per-
254 pendicular to the incident beam.
255 2.4. Confocal laser scanning microscopy (CLSM)
256 CLSM was used as one of the techniques for visualiza-
257 tion of morphologies and nanostructures of thin lms
258 [45,46]. CLSM of thin-lm samples was conducted on a
Fig. 2. Schematic illustration of the GIXS measurement. h
IN
denotes the
incident angle, 2h the diffraction angle (relative to the sample-detector
axis). The propagation direction of the incident X-ray is dened as the Y
axis, the out-of-plane (OOP) direction as the Z axis, and in-plane (IP)
direction perpendicular to the Y axis as the X axis. Q
X
and Q
Z
are the
components of the scattering vector along the IP (X axis) direction and the
OOP (Z axis) direction, respectively. For samples subjected to rubbing and
annealing treatments and thus having anisotropic in-plane characteris-
tics, GIXS was conducted in two different congurations: (i) the propa-
gation direction of the incident X-ray was parallel (aligned) with the
rubbing direction (x= 0); (ii), the rubbing direction was rotated away
from the propagation direction of the incident X-ray by 90 (i.e., x= 90),
thus perpendicular to the incident beam.
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259 Leica TCS SP5 confocal laser scanning microscope system
260 (Leica Microsystems) using an 100X oil-immersion objec-
261 tive. The system used a linearly polarized diode UV laser
262 at 405 nm as the excitation source and a spectral PMT as
263 the detector. The scanning rate is 400 Hz, and the step size
264 is 40 nm. The optical resolution of CLSM can be optimized
265 to 200 nm. Three thin-lm samples (either before or after
266 rubbing and annealing treatments) were investigated: neat
267 lms of F(MB)5 (host), neat lms of Pt(II) complexes
268 (guest), and mixture lms of F(MB)5:Pt(II) complexes.
269 The spectral window of the PMT was set at 420460 nm
270 for collecting the (blue) luminescence CLSM image of the
271 host material [F(MB)5], and at 600700 nm for collecting
272 the (red) luminescence CLSM image of the guest material
273 [Pt(II) complex aggregates]. For oriented thin-lm samples,
274 polarization-dependent CLSM was studied by aligning the
275 polarization of the excitation laser either parallel (//) or
276 perpendicular (\) to the rubbing direction.
277 2.5. Variable-angle spectroscopic ellipsometry
278 Variable-angle spectroscopic ellipsometry (VASE) in the
279 reection mode was used to study the optical constants of
280 thin lms of neat N200 for verifying the in-plane and out-
281 of-plane anisotropy absorption of the columnar stacking.
282 Ellipsometry measures the change in polarization of light
283 as a function of incident angle and wavelength [6,47,48].
284 The experimentally determined ellipsometric parameters
285 are W and D, which are related to the ratio of Fresnel
286 reection coefcients R
p
and R
s
for p- and s-polarized light,
287 respectively, by R
p
/R
s
= tan(W) e
iD
. Optical constants of the
288 materials are then determined by rst constructing an
289 optical model of the sample with physically meaningful
290 structural and optical parameters, and then by iteratively
291 adjusting these parameters to obtain the best t to the
292 measured ellipsometric data by minimizing the mean
293 square error (MSE) [47]. Ellipsometry over a wavelength
294 range of 2701100 nm in 5 nm steps was performed in
295 air using the J.A. Woollam V-VASE spectroscopic ellipsom-
296 eter equipped with a xenon lamp source. The angles of
297 incidence used were between 65 and 75 relative to the
298 surface normal in steps of 5. The nonlinear regression
299 analysis of the measured ellipsometric data was performed
300 using the J.A. Woollam WVASE32 software.
301 3. Results and discussions
302 3.1. GIXS and ellipsometric analyses of neat lms of Pt(II)
303 complexes
304 Fig. 3 presents the 2D GIXS images of the neat N200
305 lms under three different conditions: (a) as-deposited,
306 without rubbing and annealing treatments, (b) after
307 rubbing and annealing treatments, measured with the
308 incident X-ray parallel to the rubbing direction (x= 0),
309 and (c) after rubbing and annealing treatments, measured
310 with the incident X-ray perpendicular to the rubbing direc-
311 tion (x= 90). As can be seen in Fig. 3(a), even for the as-
312 deposited lm (without rubbing and annealing
313 treatments), there are already clear X-ray scattering pat-
314 terns, conrming the formation of N200 aggregates in the
315 as-deposited neat lm. Although not very strong, in
316 Fig. 3(a), one can observe a pattern representing the Pt
317 Pt stacking around Q
x
= 19
1
. It indicates that the N200
318 Pt complexes tend to self-assemble into columnar stacks
319 in the as-cast lm. In addition, the PtPt signal only ap-
Fig. 3. 2D GIXS images of the neat N200 lms under three different
conditions: (a) as-deposited, without rubbing and annealing treatments,
(b) after rubbing and annealing treatments, measured with the incident
X-ray parallel with the rubbing direction (x= 0), and (c) after rubbing
and annealing treatments, measured with the incident X-ray perpendic-
ular to the rubbing direction (x= 90).
4 Y.-T. Tsai et al. / Organic Electronics xxx (2013) xxxxxx
ORGELE 2380 No. of Pages 11, Model 3G
25 November 2013
Please cite this article in press as: Y.-T. Tsai et al., Analyzing nanostructures in mesogenic hostguest systems for polarized phosphores-
cence, Org. Electron. (2013), http://dx.doi.org/10.1016/j.orgel.2013.11.025
320 pears in the in-plane direction (i.e., along Q
x
), not observed
321 in the out-of-plane direction (i.e., along Q
z
). It suggests that
322 the columnar axis lies on the substrate surface. In Fig. 3(a),
323 one also observes GIXS patterns at smaller Qs, which
324 represent the inter-column assembly structure of the
325 aggregates. The more ring-like GIXS patterns at smaller
326 Qs, however, indicate a somewhat random distribution
327 of the inter-column structures.
328 As seen in Fig. 3(b) and (c), upon rubbing and thermal
329 annealing, the signals representing PtPt stacking become
330 sharper and stronger, indicating growth in aggregate size.
331 Again, the PtPt signals still appear only in the in-plane
332 direction (i.e., at Q
x
19
1
), not observed in the out-of-
333 plane direction (i.e., along Q
z
). As Fig. 3(b) is compared
334 with Fig. 3(c), GIXS signals at smaller Qs converge into
335 specic peaks (dots) and are signicantly enhanced with
336 rubbing and annealing. The observed GIXS patterns indi-
337 cate that aggregates grow in size and adopt better orga-
338 nized inter-column structures and orientation as a result
339 of rubbing/annealing. Moreover the better organized struc-
340 tures are preserved upon subsequent cooling. Examining
341 the GIXS patterns in Fig. 3(b) and (c) reveals that the
342 assembly of the Pt complexes has the tetragonal columnar
343 structure (Col
t
), whose packing structure and assignment
344 of Miller indices are illustrated in Fig. 4. Note that Liao
345 et al. [30] had reported that similar Pt complexes, although
346 exhibiting the hexagonal columnar mesophase at higher
347 temperatures (>240 C), did exhibit the rectangular/tetrag-
348 onal columnar mesophase at lower temperatures (<240 C,
349 like the case here). For convenience, the [100] is assigned
350 along the PtPt stacking direction, while [010] and [001]
351 are assigned for the two inter-column packing directions.
352 With the emerging assembly structure and indexing sys-
353 tem, the GIXS peaks in Fig. 3(b) and (c) can now be unam-
354 biguously assigned as such. Reections occurring along the
355 out-of-plane orientation that represent the out-of-plane
356 inter-column packing can be assigned [001] and higher-
357 order ones, while reections occurring along the in-plane
358 orientation that represent in-plane inter-column packing
359 can be assigned [010] and higher-order ones.
360 Anisotropic characteristics of the aggregates of Pt com-
361 plexes in rubbed and annealed samples can be further ana-
362 lyzed by considering different packing orientations
363 through comparing GIXS images detected with the inci-
364 dent X-ray parallel to the rubbing direction (i.e., GIXS at
365 x= 0, Fig. 3(b)) to those detected with the incident
366 X-ray perpendicular to the rubbing direction (i.e., GIXS at
367 x= 90, Fig. 3(c)). Fig. 5 shows three possible columnar
368 packing orientations relative to the surface and the
369 rubbing direction. In case A, the columns (or intra-column
370 PtPt stacking) are vertical to the surface and the inter-
371 column packing is along the surface. In such a case, ideally
372 in GIXS one would only observe the PtPt stacking signal
373 along the OOP direction (i.e., along Q
z
) but not along the
374 IP direction (i.e., along Q
x
). In addition, one would also
375 observe no inter-column packing signal (i.e., [001] or
376 [010]) along the OOP direction. In case B, columns (or in-
377 tra-column PtPt stacking) are parallel to the surface and
378 the rubbing direction, while one inter-column packing
379 direction (i.e., [001]) is along the OOP direction and
380 another (i.e., [010]) is perpendicular to the rubbing direc-
381 tion. In such a case, ideally in 2D GIXS one would observe
382 no PtPt stacking signal along the OOP direction, and
383 whether the PtPt stacking signal along the IP direction
384 can be observed depends on x (0 or 90). At x= 0, one
385 would observe inter-column packing signals [001]/[010]
386 along the OOP/IP direction, respectively, but no PtPt
387 signal along the IP direction (i.e., along Q
x
) since the
388 PtPt packing is along the Y direction under such a mea-
389 surement conguration (thus cannot be easily resolved
390 by the 2D GIXS). On the other hand, by rotating the sample
391 to make x= 90, one shall now observe (001)/PtPt stack-
392 ing signal along the OOP/IP direction, respectively, but no
393 [010] signal along the IP direction since the [010] orienta-
394 tion is now along the Y direction. In case C, columns (or in-
395 tra-column PtPt packing) are parallel with the surface but
396 perpendicular to the rubbing direction, while one inter-
397 column packing direction (i.e., [001]) is along the OOP
398 direction and another (i.e., [010]) is parallel with the
399 rubbing direction. In such a case, ideally in 2D GIXS one
400 would observe no PtPt stacking signal along the OOP
401 direction, while whether the PtPt stacking signal can be
402 observed again depends on x (0 or 90). At x= 0, one
403 would observe [001]/PtPt stacking signal along the
404 OOP/IP direction, respectively, but no [010] signal along
405 the IP direction since the [010] orientation is along the Y
406 direction. On the other hand, at x= 90, one shall now
407 observe inter-column packing signals [001]/[010] along
408 the OOP/IP direction, respectively, but no PtPt signal
409 along the IP direction since the PtPt packing is now along
410 the Y direction.
411 Since in GIXS images of Fig. 3(b) and (c) one sees clear
412 inter-column packing signal [001] but no intra-column
413 PtPt stacking signal along the OOP direction (i.e., along
414 Q
z
), the packing orientation case A can be excluded. Obser-
415 vation of the PtPt stacking signal mainly along the IP
416 direction suggests packing orientations of cases B and C.
417 Cases B and C can be further distinguished by comparing
418 GIXS images collected under x= 0 and x= 90 congura-
419 tions. Fig. 6 shows the in-plane proles (i.e., along Q
x
) of
420 the three GIXS images in Fig. 3(a)(c), with the PtPt stack-
421 ing signal (i.e., at Q
x
19
1
) being enlarged and shown in
422 the inset. In the inset of Fig. 6, one sees that for the sample
423 subjected to the rubbing and annealing treatments, the
424 PtPt signal detected with x= 0 is stronger than that de-
425 tected with x= 90. In addition, for the sample subjected
426 to the rubbing and annealing treatments, the (010) signal
Fig. 4. The packing structure of the tetragonal columnar structure (Col
t
)
and the assignment of Miller indices.
Y.-T. Tsai et al. / Organic Electronics xxx (2013) xxxxxx 5
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427 detected with x= 0 is signicantly weaker than that
428 detected with x= 90. These results indicate that, with
429 the rubbing and annealing treatments: (i) the stacking col-
430 umns of the Pt(II) complexes appear to have the preferen-
431 tial orientation perpendicular to the rubbing direction; (ii)
432 the in-plane inter-column packing (i.e., [010] orientation)
433 is preferentially along the rubbing direction. That is, among
434 the three possible column packing orientations relative to
435 the surface and the rubbing direction illustrated in Fig. 5,
436 case C represents the preferential column packing orienta-
437 tion, although the intra-column packing (i.e., PtPt) and
438 inter-column packing (i.e. [010]) perhaps are not perfectly
439 aligned relative to the rubbing direction and there is some
440 distribution between cases B and C. Such results are con-
441 sistent with previous results of polarized optical spectros-
442 copy (i.e., polarized photoluminescence and absorption) of
443 neat lms of Pt complexes subjected to rubbing and
444 annealing treatments [29]. Previous results of polarized
445 optical spectroscopy showed that the polarization of the
446 MMLCT absorption and emission (and thus the columnar
447 PtPt stacking) were more along the direction perpendicu-
448 lar to the rubbing direction, while the absorption associ-
449 ated with the pyridyl azolate ligands (and thus the
450 molecular plane of the discotic Pt complex) was more
451 along the rubbing direction.
452 From GIXS patterns of the rubbed and annealed samples
453 shown in Fig. 3(b) and (c), the d spacings along the intra-
454 column PtPt stacking direction (d
PtPt
), along the inter-
455 column [001] direction (d
0 0 1
), and along the inter-column
456 [010] direction (d
0 1 0
) are calculated based on Braggs law
457 [49] and are listed in Table 1. Furthermore, the average
458 dimensions of the aggregates/grains along the above differ-
459 ent packing directions (i.e., L
PtPt
, L
0 0 1
, L
0 1 0
) are also esti-
460 mated using the Scherrer grain-size analysis [50] and are
461 also listed in Table 1. Note that the calculated d
0 1 0
of
462 22.22 is close to that of d
0 0 1
of 22.62 , and that both
463 are about

2
p
times the d spacing along the [011] direction
464 (15.48 , not listed in Table 1), consistent with the
465 assignment of the packing structure to the tetragonal
466 columnar structure. The calculated inter-column spacing
467 of 22.4 0.2 is shorter than the molecular length
468 (29.19 ), but longer than the rigid core length of
469 16.24 , suggesting the discotic Pt complexes are assem-
470 bled into the columnar organization with a tilted format
471 relative to the inter-column [001] and [010] orientations.
472 The intra-column PtPt stacking distance (d
PtPt
) is calcu-
473 lated to be 3.33 , which is well within the PtPt distances
474 allowing strong MMLCT transitions to occur [51,52]. On the
475 other hand, with L
PtPt
= 43.33 , L
0 0 1
= 274.47 , and
476 L
0 1 0
= 206.48 in the rubbed and annealed neat lms,
477 one estimates the average size of the aggregates/grains to
478 be 13 Pt complexes along the PtPt stacking direction,
479 12 columns along the inter-column [001] direction and
480 910 columns along the inter-column [010] direction.
481 The Scherrer grain-size analysis also shows that the assem-
482 bly size of Pt complexes had grown with rubbing and
483 annealing treatment. For instance, L
PtPt
had grown from
484 26 of the as-deposited neat lm to 43.33 of the
485 rubbed and annealed lm.
486 From the above GIXS analyses, it has been established
487 that in the rubbed and annealed neat lms of N200, the
488 structure and orientational alignment of the molecular
489 assembly is inclined toward case C described in Fig. 5. In
490 addition, it is deduced that the discotic Pt complexes are
491 assembled into the columnar organization with a tilted for-
492 mat relative to the inter-column [001] and [010] orienta-
493 tions. Such anisotropic molecular assembly can be further
494 veried by characterizing the anisotropic optical properties
495 of rubbed and annealed neat lms originating from the
496 MMLCT transitions and ligand-centered transitions (utiliz-
497 ing the variable-angle spectroscopic ellipsometry-VASE).
498 Good ttings to the experimentally measured ellipsometric
499 values Wand D could be obtained by using a biaxial model
500 for refractive indices and extinction coefcients, which in
501 turn were constructed by a KramersKronig consistent
Fig. 5. Three possible/representative column packing orientations (of the tetragonal columnar assembly) relative to the surface and the rubbing direction.
Fig. 6. In-plane proles (i.e., along Q
x
) of the three GIXS images in
Fig. 3(a)(c), with the PtPt stacking signal (i.e., around Q
x
19
1
)
being enlarged and shown in the inset.
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502 model using a combination of one Cauchy background and
503 several Gaussian oscillators. Fig. 7 shows the extracted
504 absorption coefcients converted fromthe extracted aniso-
505 tropic extinction coefcients for the rubbed and annealed
506 neat lmof N200. a
//,IP
, a
\,IP
, and a
OOP
represent the absorp-
507 tion coefcients for the in-plane absorption coefcient
508 along the rubbing direction, the in-plane absorption
509 coefcient perpendicular to the rubbing direction, and the
510 out-of-plane absorption coefcient, respectively. One notes
511 that a
//,IP
and a
\,IP
agree well with the normal-incidence
512 absorption spectra of the uniaxially rubbed N200 lmmea-
513 sured with the polarization parallel (//) and perpendicular
514 to (\) the rubbing direction (inset of Fig. 7, [29]), respec-
515 tively, inspiring additional condence in the anisotropic
516 optical constants obtained. For the low-energy MMLCT
517 transition region (e.g., 520600 nm), the strongest and clear
518 absorption peak in a
\,IP
, weaker a
//,IP
, and nearly zero a
OOP
519 are consistent with the foregoing interpretation that the
520 PtPt stacking orientation is most likely case C of depicted
521 in Fig. 5, mingled with a bit of case B, and hardly any case
522 A, since the MMLCT transition is typically along the chain
523 of the metal cores [53]. For the higher-energy ligand-cen-
524 tered transition region (e.g., 300 nm), both a
//,IP
and a
OOP
525 are larger thana
\,IP
, withthe dichroic ratio of >2, whichsug-
526 gests that in the aligned neat lms of Pt(II) complexes, the
527 pyridyl azolate ligands with alkyloxyphenyl groups are
528 roughly along the surface expanded by the rubbing and
529 the OOP directions (with certain tilting relative to the sur-
530 face). Again, the residual a
\,IP
suggests the alignment is
531 not perfect and there is certain mixture of case B and case
532 C (Fig. 5).
533 3.2. GIXS analyses of host: guest mixture lms
534 Fig. 8 shows the 2D GIXS images of the F(MB)5:N200
535 mixture lms coated over PEDOT:PSS under three different
536 conditions: (a) without alignment treatment, (b) with
537 alignment treatment, measured with the incident X-ray
538 parallel with the rubbing direction (x= 0), and (c) with
539 alignment treatment, measured with the incident X-ray
540 perpendicular to the rubbing direction (x= 90). In
541 Fig. 8(a), for the F(MB)5:N200 mixture lm on PEDOT:PSS
542 without alignment treatment, no specic GIXS patterns
543 (e.g., peaks, rings etc.) associated with N200 assembly
544 can be detected, except for the cloudy background.
545 Although previous photoluminescence studies indicate
546 there is PtPt stacking and MMCLT emission of N200 even
547 in the pristine F(MB)5:N200 mixture lms subjected to no
548 alignment, the sizes and/or quantities of the N200 assem-
549 blies are probably not sufcient and the orientations are
550 probably too random to be detected by GIXS. Comparison
551 of Fig. 8(a) and Fig. 3(a) also suggests the presence of the
552 unoriented F(MB)5 host signicantly disturbs the assem-
553 bly/stacking of the Pt complex N200.
554 As seen in Fig. 8(b) and (c), for the mixture lm
555 subjected to alignment, the signal representing PtPt
556 stacking (at Q
x
19
1
) of N200 appears, indicating
557 growth of N200 aggregates. Again, the PtPt signals still
558 appear only in the in-plane direction (i.e., at Q
x
19
1
),
559 not observed in the out-of-plane direction (i.e., along Q
z
).
560 Moreover, alignment produced signals representing the in-
561 ter-column packing (i.e., peaks at smaller Qs) that suggest
562 growth of N200 aggregates and adoption of more orga-
563 nized inter-column structures and orientation within the
564 oriented F(MB)5 host. Overall, the GIXS pattern of the
565 aligned F(MB)5:N200 mixture lm is similar to that of
566 the rubbed/annealed neat N200 lm (Fig. 3(b) and (c)),
567 indicating that N200 assemblies in both cases have similar
568 PtPt stacking, inter-column structure (i.e., tetragonal
569 columnar structure, Col
t
), and orientation/alignment. As
570 such, Miller indices of GIXS peaks in Fig. 8(b) and (c) can
571 be assigned in a way similar to that in Fig. 3(b) and (c),
572 with the [100] being for the PtPt stacking direction,
573 [001] and higher-order ones being for reections and
574 inter-column packing along the out-of-plane orientation,
575 [010] and higher-order ones being for reections and
576 inter-column packing along the in-plane orientation.
Table 1
Packing parameters of N200 assemblies/aggregates in lms with different compositions and processing/treatment conditions, including the d spacings along
the intra-column PtPt stacking direction (d
PtPt
), along the inter-column [001] direction (d
0 0 1
), and along the inter-column [010] direction (d
0 1 0
), and the
average dimensions of the aggregates/grains along the above different packing directions (i.e., L
PtPt
, L
0 0 1
, L
0 1 0
).
d
PtPt
() L
PtPt
() d
0 0 1
() L
0 0 1
() d
0 1 0
() L
0 1 0
()
N200 no treatments 3.34 25.97 22.36 183.19 22.15 184.82
N200 with treatments 3.33 43.33 22.62 274.47 22.22 206.48
F(MB)5:N200 no treatments
F(MB)5:N200 with treatments 3.35 18.96 23.68 143.21 22.10 121.62
Fig. 7. Extracted absorption coefcients converted from the extracted
anisotropic extinction coefcients for the rubbed and annealed neat lm
of N200. a
//,IP
, a
\,IP
, and a
OOP
represent the absorption coefcients for the
in-plane absorption coefcient along the rubbing direction, the in-plane
absorption coefcient perpendicular to the rubbing direction, and the
out-of-plane absorption coefcient, respectively. The inset shows the
normal-incidence absorption spectra of the uniaxially rubbed N200 lm
measured with the polarization parallel with (//) and perpendicular to (\)
the rubbing direction.
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577 Fig. 9 shows the in-plane proles (i.e., along Q
x
) of the
578 three GIXS images in Fig. 8(a)(c), with the PtPt stacking
579 signal (i.e., around Q
x
19
1
) being enlarged and shown
580 in the inset. As in the case of the neat N200 lm, for the
581 sample subjected to the rubbing and annealing treatments,
582 the PtPt signal detected with x= 0 is stronger than that
583 detected with x= 90. In addition, the inter-column [010]
584 signal detected with x= 0 is signicantly weaker than
585 that detected with x= 90. Thus in the mixture lm, with
586 the alignment treatment, the N200 assemblies in the
587 F(MB)5 host also preferentially adopt the column packing
588 orientation (relative to the rubbing direction and the sur-
589 face) like case C in Fig. 5, although the alignment is imper-
590 fect (i.e., there may be some distribution between case B
591 and case C). Such results are consistent with previous
592 results of polarized optical spectroscopy (i.e., polarized
593 photoluminescence) of the F(MB)5:N200 mixture lms
594 subjected to alignment treatments [29]. Previous results
595 of polarized optical spectroscopy showed that the polariza-
596 tion of the MMLCT emission (and thus the columnar PtPt
597 stacking) of N200 guests were more perpendicular to the
598 rubbing direction, while the F(MB)5 host emission was
599 more along the rubbing direction (i.e., F(MB)5 host
600 molecules are aligned along the rubbing direction).
601 Although F(MB)5 host molecules are oriented on the align-
602 ment-treated surface, yet no GIXS signals associated with
603 F(MB)5 can be detected. It is perhaps because F(MB)5
604 possess a very short intermolecular correlation length not
605 readily detectable by GIXS.
606 From GIXS patterns of the rubbed and annealed samples
607 shown in Fig. 8(b) and (c), the d spacings d
PtPt
, d
0 0 1
, and
608 d
0 1 0
for the aligned mixture lm are calculated and are
609 listed in Table 1. One notices that these d spacing values
610 are similar to those in the N200 neat lms, conrming sim-
611 ilar assembly structures in both cases. The average dimen-
612 sions of the N200 aggregates in mixture lms along the
613 above different packing directions (i.e., L
PtPt
, L
0 0 1
, L
0 1 0
)
614 are also estimated and are also listed in Table 1. On the
615 other hand, with L
PtPt
= 18.96 , L
0 0 1
= 143.21 , and
616 L
0 1 0
= 121.62 in the aligned mixture lms, one estimates
617 the average size of the aggregates at 56 Pt complexes
618 along the PtPt stacking direction, 6 columns along the
619 inter-column [001] direction and 56 columns along
620 the inter-column [010] direction. From results of Table 1,
621 one might speculate that although the nematic F(MB)5
Fig. 8. 2D GIXS images of the F(MB)5:N200 mixture lms coated over
PEDOT:PSS under three different conditions: (a) without no alignment
treatments, (b) with alignment treatments, measured with the incident
X-ray parallel with the rubbing direction (x= 0), and (c) with alignment
treatment, measured with the incident X-ray perpendicular to the
rubbing direction (x= 90).
Fig. 9. In-plane proles (i.e., along Q
x
) of the three GIXS images in
Fig. 8(a)(c), with the PtPt stacking signal (i.e., around Q
x
19
1
)
being enlarged and shown in the inset.
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622 host can guide the alignment of the N200 aggregates in the
623 mixture lm, the presence of the F(MB)5 hosts disturbs
624 the assembly of the Pt complex N200, thereby reducing
625 the sizes of N200 aggregates to nearly half.
626 3.3. CLSM
627 Although the resolution of CLSM used might not be
628 sufcient to quantify the nanostructures encountered in
629 this study, the CLSM images were collected as supportive
630 information for aggregates of N200 and the nanoscale
631 phase separation in the F(MB)5:N200 mixture lms.
632 Fig. 10(a) and (b) show the luminescence CLSM images
633 of the neat F(MB)5 lm and the neat N200 lm, respec-
634 tively, either without (panel (i)) or with (panels (ii) and
635 (iii)) rubbing/annealing treatments. For the aligned
636 thin-lm samples (i.e., with rubbing/annealing), polariza-
637 tion-dependent CLSM images were taken by aligning the
638 polarization of the excitation laser either perpendicular
639 (\, panel (ii)) or parallel to (//, panel (iii)) the rubbing
640 direction. In panel (i) of Fig. 10(a), one sees that CLSM im-
641 age of the neat F(MB)5 lm without rubbing/annealing is
642 homogeneous, as expected of an amorphous/glassy organic
643 lm. With rubbing and annealing, the image of the // polar-
644 ization (panel (iii) of Fig. 10(a)) becomes signicantly
645 stronger than that of \ polarization in panel (ii) of
646 Fig. 10(a) (as expected), and yet the CLSM images are still
647 generally homogeneous (except for a few spots associated
648 with non-ideal rubbing/alignment). In contrast, in panel (i)
649 of Fig. 10(b), one observes a grainy CLSM image even in the
650 neat N200 lm without rubbing/annealing, indicating
651 formation of aggregates/grains as coated. With rubbing
652 and annealing (panels (ii) and (iii) of Fig. 10(b)), in addition
653 to polarization dependence of CLSM images (due to align-
654 ment), one clearly sees substantial growth of domains.
655 Fig. 11(a) and (b) show the luminescence CLSM images
656 of the F(MB)5 emission and the N200 MMLCT emission
657 taken from a same F(MB)5:N200 mixture lm, respec-
658 tively, either without (panel (i)) or with (panels (ii) and
659 (iii)) rubbing/annealing treatments. For the aligned thin-
660 lm samples (i.e., with rubbing/annealing), polarization-
661 dependent CLSM images were taken by aligning the
662 polarization of the excitation laser either perpendicular
663 (\, panel (ii)) or parallel to (//, panel (iii)) the rubbing
664 direction. In panel (i) of Fig. 11(a) and (b), one observes
665 grainy CLSM images for both F(MB)5 emission and N200
666 MMLCT emission even in mixture lms without rubbing/
667 annealing, indicating certain extent of phase separation.
668 With rubbing and annealing (panels (ii) and (iii) of
669 Fig. 11(a) and (b)), in addition to polarization dependence
670 of CLSM images (due to alignment), again one sees signi-
671 cant growth of phase-separated domains and N200 aggre-
672 gates/grains, which is consistent with the observation in
673 GIXS. In CLSM images of the aligned hostguest mixture
674 lms, //-polarization N200 MMLCT emission (panel (iii) of
675 Fig. 11(b)) can be somewhat detected, although weaker
676 than the \-polarization emission (panel (ii) of Fig. 11(b)).
677 It is perhaps due to imperfect alignment of guest
678 aggregates as suggested by GIXS.
Fig. 10. Luminescence CLSM images of (a) the neat F(MB)5 lm and (b)
the neat N200 lm, either without (panel (i)) or with (panels (ii) and (iii))
rubbing/annealing treatments. For the aligned thin-lm samples (i.e.,
with rubbing/annealing), polarization-dependent CLSM images were
taken by aligning the polarization of the excitation laser either perpen-
dicular to (\, panel (ii)) or parallel with (//, panel (iii)) the rubbing
direction.
Fig. 11. Luminescence CLSM images of (a) the F(MB)5 emission and (b)
the N200 MMLCT emission taken from a same F(MB)5:N200 mixture lm,
either without (panel (i)) or with (panels (ii) and (iii)) rubbing/annealing
treatments. For the aligned thin-lm samples (i.e., with rubbing/anneal-
ing), polarization-dependent CLSM images were taken by aligning the
polarization of the excitation laser either perpendicular to (\, panel (ii))
or parallel with (//, panel (iii)) the rubbing direction.
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679 4. Conclusions
680 The GIXS and CLSM analyses were conducted to fur-
681 nish new insight into molecular self-assembly, orienta-
682 tion and the resultant nanostructures in four distinct
683 cases: (a) N200 neat lm without rubbing/annealing
684 treatments, (b) N200 neat lm with rubbing/annealing
685 treatments, (c) F(MB)5:N200 mixture lm without rub-
686 bing/annealing treatments, and (d) F(MB)5:N200 mixture
687 lm with rubbing/annealing treatments. These combined
688 experimental observations led to the lm morphologies
689 as depicted in Fig. 12. In the as-cast neat N200 lm
690 (Fig. 12(a)), GIXS patterns suggest aggregates of N200
691 have readily formed, although their sizes are relatively
692 smaller and orientations are somewhat random. Rubbing
693 and annealing induce growth and better organized orien-
694 tation of the N200 aggregates (Fig. 12(b)). Examining the
695 GIXS patterns of rubbed/annealed N200 neat lms re-
696 veals that the assembly of the Pt complexes has the
697 tetragonal columnar structure (Col
t
). With the rubbing
698 and annealing treatments, the columnar stacks of the
699 Pt(II) complexes appear largely oriented perpendicular
700 to the rubbing direction with the in-plane inter-column
701 packing (i.e., [010] orientation) preferentially along the
702 rubbing direction. Such results are consistent with those
703 previously deduced from polarized optical spectroscopy
704 of N200 lms. For the F(MB)5:N200 mixture lm without
705 rubbing and annealing treatments (Fig. 12(c)), although
706 previous photophysical studies indicate PtPt stacking
707 and MMCLT emission of N200, no specic signals associ-
708 ated with N200 assembly can be detected in its GIXS
709 patterns. It suggests the presence of the (un-oriented)
710 F(MB)5 host signicantly disturbs the assembly of the
711 Pt(II) complex, so that the sizes and/or quantities of
712 the N200 assemblies are probably not sufcient and
713 the orientations are probably too random for GIXS to de-
714 tect. For the mixture lm subjected to alignment
715 (Fig. 12(d)), again the signals associated with assemblies
716 of N200 (similar to those observed for rubbed/annealed
717 neat N200 lms) appear, indicating the growth of N200
718 aggregates and adoption of more organized inter-column
719 structures and orientation within the aligned F(MB)5
720 host. The organization and alignment are presumably in-
721 duced by the oriented F(MB)5 host oligomers on the
722 rubbed PEDOT:PSS alignment layer. Overall, the GIXS
723 pattern of the aligned F(MB)5:N200 mixture lm is sim-
724 ilar to that of the rubbed/annealed neat N200 lm. It
725 indicates that N200 assemblies in aligned mixture lms
726 have PtPt stacking, inter-column structure (i.e., tetrago-
727 nal columnar structure, Col
t
), and orientation/alignment
728 similar to those in aligned neat N200 lms, although
729 the Scherrer grain-size analysis reveals that the aggre-
730 gate sizes in the mixture lms are smaller than those
731 in N200 neat lms.
(a) Neat N200, no treatments (b) Neat N200, with treatments
(c) F(MB)5:N200, no treatments (d) F(MB)5:N200, with treatments
Fig. 12. Schematic representations of the morphologies and molecular alignments of: (a) N200 neat lm without rubbing/annealing treatments, (b) N200
neat lm with rubbing/annealing treatments, (c) F(MB)5:N200 mixture lm without rubbing/annealing treatments, and (d) F(MB)5:N200 mixture lm with
rubbing/annealing treatments.
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732 Acknowledgements
733 The authors gratefully acknowledge the nancial
734 support from National Science Council and Ministry of
735 Education of Taiwan (under the Grant NSC 98-2120-M-
736 002-005, NSC 99-2221-E-002-118-MY3, NSC 102-2221-E-
737 002-203-MY3, and NTU-CESRP-102R7607-2).
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Please cite this article in press as: Y.-T. Tsai et al., Analyzing nanostructures in mesogenic hostguest systems for polarized phosphores-
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