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Article
Effect of Solvent Exchange at the Bi-Phasic Dip-Coating
Interface on the Formation of Polythiophene Thin Films
Gun Woo Kim, Min Kim, and Yeong Don Park
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b11534 • Publication Date (Web): 11 Jan 2018
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The Journal of Physical Chemistry C is published by the American Chemical Society.


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Page 1 of 29 The Journal of Physical Chemistry

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4 Effect of Solvent Exchange at the Bi-Phasic Dip-Coating
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Interface on the Formation of Polythiophene Thin Films
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9 Gun Woo Kim,a† Min Kimb† and Yeong Don Parka,*
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11 Department of Energy and Chemical Engineering, Incheon National University, Incheon
12 22012, Korea
13 b
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Center for Nano Science and Technology @Polimi, Istituto Italiano di Tecnologia, Via
15 Giovanni Pascoli 70/3, 20133 Milan, Italy
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17 *Corresponding authors: ydpark@inu.ac.kr (ydp)
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† G. W. Kim and M. Kim contributed equally to this work.
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23 Abstract
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25 The bi-phasic dip-coating method reduces the amount of solution required for coating by using a
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27 phase-separated bi-phasic solvent system and is highly promising for the preparation of large-
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area thin films with applications in electronic devices. We studied the effects of varying the
30 miscibility of the low-lying secondary solvent and the high-lying polymer-dissolving solvent on
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32 polymer crystallization and on the resulting films. We systematically chose three kinds of
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34 solvents with high density for use as the low-lying solvent phase and compared the miscibilities
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of the low-lying solvents and the high-lying polymer solution in terms of their Hansen solubility
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37 parameters (HSPs). We demonstrated that the HSP distance is correlated with the degree of
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39 intermixing of the low-lying and high-lying solvents, and determined the effects of intermixing
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41 on polymer aggregation and stability in the solution state for various aging times. The degree of
42 solvent exchange at the interface also determines the film morphology and charge carrier
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44 mobility of the resulting dip-coated P3HT thin film. This study confirms the potential of bi-
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46 phasic dip-coating as a scalable film preparation method for use in large-area flexible electronics.
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3 Introduction
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Organic field-effect transistors (OFETs) have been investigated extensively over the past
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9 two decades because of their potential applications in flexible, wearable, and biointegratable
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11 electronics.1-3 Electronics printing is a promising technology that enables the rapid fabrication of
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integrated OFETs over large areas with sophisticated circuits with low-cost solution processes.4
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16 Various reliable solution-printing techniques for the fabrication of electronics have been
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18 developed, e.g., doctor blade coating, bar coating, ink-jet printing, and dip-coating.5 These
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20 techniques have been optimized to yield polymer thin films with uniform and smooth
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23 morphologies and desirable crystal structures as well as molecular orientations that ensure
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25 efficient charge transport in OFET devices.6-10
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27 Among these solution-processing approaches, the dip-coating technique has been
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extensively utilized in both academic research and industrial production.11-12 The fine control that
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32 is possible with the dip-coating technique enables not only the preparation of uniform large-area
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34 polymer thin films with low roughness on various curved templates but also the self-assembly of
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conjugated polymers for efficient charge carrier transport.13-18 However, the dip-coating process
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39 also has a drawback that limits its range of utilization and makes scaling it up difficult: a large
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41 volume of polymer solution is normally required to fill the reservoir. To overcome this problem,
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43 a new dip-coating method known as bi-phasic dip-coating that uses a phase-separated solvent
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46 system, in which the useless main part of the chemical solution is replaced with an indefinitely
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48 reusable inert liquid phase, has been developed.19-21 In this configuration, the coating of large
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50 surfaces can be achieved from a minimal solution volume.
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To implement bi-phasic dip-coating, it is vital to select a suitable pair of solvents that can
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55 form a stabilized bi-phasic state. This bi-phasic state can be produced by using a solvent with low
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3 density and a solvent with high density.19 Even though the bi-phasic state remains stable for a
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long time, the pair of solvents will intermix at the bi-phasic interface to some degree, which
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8 means that the polymer material dissolved in the upper solution will be affected by the solvent in
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10 the low-lying phase. The molecular conformation of the crystalline polymer and its self-assembly
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in the solution state are likely to influence not only the resulting film morphology but also its
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15 molecular order.22-26 Therefore, it is of high importance to study the effects in the bi-phasic state
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17 of the low-lying solvent with high density on the upper polymer solution with low density, which
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19 thus far has rarely been studied.
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22 In this study, we systematically investigated the effects in bi-phasic dip-coating of varying
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24 the low-lying secondary solvent on the upper conjugated polymer solution and the resulting
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26 polymer thin films. We compared three chlorinated solvents, chloroform (CF), chlorobenzene
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(CB), and dichlorobenzene (DCB), which were selected as the low-lying solvents because of their
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31 variation in density. Xylene (Xyl) was selected as the high-lying solvent for the upper phase, in
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33 which poly(3-hexylthiophene) (P3HT) dissolves completely at an elevated temperature. We
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monitored the aggregation of P3HT in the upper solution as a function of the aging time and
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38 determined the influence on this process of the three low-lying solvents. We demonstrated that
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40 the interaction between the two solvents strongly affects the aggregation of the P3HT phase as
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42 well as the stability of the bi-phasic system, which ultimately determine the crystalline structure
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45 and uniformity of the resulting P3HT thin films.
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3 Experimental Section
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Preparation of Thin Films and OFET Devices: Poly(3-hexylthiophene) (P3HT, molecular weight
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8 Mw = 37 kDa) was purchased from Rieke Metals, Inc. and used without further purification.
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10 Highly doped n-type Si wafers were used as not only transistor substrates but also gate electrodes.
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Thermally grown 300 nm thick silicon dioxide (SiO2) functioned as the gate dielectric. Substrates
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15 were cleaned through ultrasonication in acetone and ethanol for 30 min each, followed by drying
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17 overnight under vacuum prior to use. Hexamethyldisilazane (HMDS) (Aldrich) was applied to
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19 each SiO2/Si substrate via spin-coating, and used as an organic interlayer material between each
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22 dielectric layer and organic active layer. 3 mL vials were filled with the high density solvents CF,
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24 CB, and DCB. Then 0.2 mL of P3HT solution (0.7 wt%) was carefully dropped onto the surface
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27 of each high density solvent. The P3HT solution in Xyl was stirred at 90℃ for 15 min to
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30 complete the dissolution. After a given bi-phasic system had been aged for various time, the 1.2-
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32 cm2 substrate (H 1.5 cm × L 0.8 cm) was withdrawn into the bi-phasic solution at a various
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34 speed (1, 3, 5, 7, 10 mm/s). The source and drain electrodes were deposited on the P3HT layers
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37 by evaporating Au through a shadow mask. Identical P3HT films were fabricated on transparent
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39 glass substrates instead of Si substrates in preparation for the UV-vis absorption measurements.
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41 Characterization: UV-vis absorption spectra were recorded by using a UV-vis
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spectrophotometer (Thermo Scientific, Genesys 10S). The thicknesses of the P3HT films were
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46 determined with an ellipsometer (J. A. Woollam Co. Inc.). The film morphologies were
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48 characterized with atomic force microscopy (AFM) (Multimode 8, Bruker) and optical
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microscopy (OM; OLYMPUS BX51). The electrical performances of the OFETs were measured
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53 by using a semiconductor analyzer (Keithley 4200-SCS) in vacuum at room temperature. The
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3 field-effect mobilities were estimated in the saturation regime from the transfer plots of drain
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current (ID) versus gate voltage (VG) according to the equation:
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8  =
( −  ) (6)

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11 where W and L are the transistor channel width (1000 µm) and length 100 µm respectively. µ is
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13 the hole mobility. VT is the threshold voltage and Ci is the capacitance per unit area of the silicon
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15 dioxide gate dielectric (10.8 × 10-9 Fcm-2).
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3 Results and Discussion
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We tested the three different solvents CF, CB, and DCB as low-lying solvents with high
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8 density in the bi-phasic dip-coating process, and used Xyl as the high-lying solvent with low
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10 density. The differences between the densities of the low- and high-lying solvents are greater than
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0.25 g cm-3.27 We examined the bi-phasic solution states formed when the P3HT:Xyl solutions
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15 are added on top of the underlying solvents with high density (Figure 1a). The bi-phasic states
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17 formed by the addition of P3HT:Xyl solution onto the high density solvents CF, CB, and DCB
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19 were all confirmed to be stable with the naked eye. If the difference between the densities of the
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22 two solvents is not sufficiently large, the interface between the two solvents collapses, which
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24 results in an unstable bi-phasic system (Figure 1b). However, some solvent intermixing occurs
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26 whenever two different solvents meet at a bi-phase interface, which will influence polymer
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aggregation in the solution state, and further affect the molecular structure in the thin film state
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31 after coating onto a substrate (Figure 1c). To visually and systematically characterize the effects
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33 of the interaction between the low- and high-lying solvents on polymer conformation, we chose
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Xyl as the solvent with lower density; P3HT has intermediate solubility in Xyl, which as time
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38 passes induces P3HT aggregation in the solution state.28-30
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40 We monitored the changes in the color of the P3HT solutions in the bi-phasic systems as
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42 functions of time (Figure 2). P3HT has intermediate solubility in Xyl, so the high-lying solvent
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45 required heating to achieve complete dissolution. Then, the color of the Xyl solution changes
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47 from orange to purple as polymer aggregations form at room temperature. After the formation of
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49 the P3HT:Xyl/CF bi-phasic solution state, the color of the P3HT:Xyl solution changes from
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orange to dark brown within a couple of minutes. However, no distinct spectral features were
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54 observed in the cases of the Xyl/CB and Xyl/DCB bi-phasic systems even after 10 minutes. The
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56 absorption spectra of the P3HT solutions in the bi-phasic Xyl/chlorinated solvent systems were
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3 recorded. The pre-dissolved P3HT:Xyl solution with a volume ratio of 0.7 were added to the
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chlorinated solvents CF, CB, and DCB (Figure 3a). Figure 3b shows that for the Xyl/CF solvent
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8 the absorption peaks related to intermolecular interactions increase in strength as a function of
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10 time. This observation is in agreement with the spectral changes for the neat Xyl solution, which
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show that P3HT aggregation increases with time. These results indicate that the use of the
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15 Xyl/CF mixed solvent induces the aggregation of P3HT molecules to an extent similar to that of
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17 the neat Xyl solvent. On the other hand, the absorption spectra of Xyl/CB and Xyl/DCB undergo
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19 no changes with aging. These results can be explained by using Hanssen solubility parameter
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22 (HSP): the HSP difference ∆δ (MPa½) is smaller for Xyl/CF, 0.9, than for Xyl/CB (1.5) and
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24 Xyl/CF (2.4), as shown in Table 1.31 Thus the high-lying solvent Xyl is expected to intermix
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26 strongly with the low-lying solvent CF and thus induce P3HT molecules to undergo solubility-
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induced aggregation. In contrast, CB and DCB are not expected to intermix with Xyl as much as
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31 CF, which thus maintains its fully solubilized state.
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33 Figure 4a shows the absorption spectra of P3HT thin films dip-coated from the bi-phasic
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solutions Xyl/CF, Xyl/CB, and Xyl/DCB with a withdrawal speed of 5 mm/s after an aging time
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38 of 1 min. In this experiment, dip-coating was performed for a solvent aging time less than 3
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40 minutes because P3HT precipitates after 3 minutes in the Xyl/CF bi-phasic system. The
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42 absorption peaks of the P3HT thin films at 580 and 608 nm are attributed to intermolecular
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45 interactions, particularly π-π transitions, and the ratios of the intensity of the (0-0) peak at 608 nm
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47 to that of the (0-2) peak at 527 nm can be correlated with their degrees of crystallinity.32-33 The
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49 intensity of the intermolecular absorption peak at 605 nm is stronger for the film processed in
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Xyl/CF than for the films processed in Xyl/CB and Xyl/DCB. We found that the ratio of the
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54 intensities of the (0-0) and (0-2) peaks is highest for the Xyl/CF film and lowest for the Xyl/DCB
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3 strongly affected by the molecular conformation of the polymer in the solution state. The
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intermixing of the solvents in the Xyl/CF bi-phasic system induces P3HT pre-aggregation, which
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8 strongly affects the properties of the resulting P3HT thin film. In contrast, the DCB solvent in the
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10 Xyl/DCB system limits the induction of P3HT crystallization by Xyl, and so the resulting thin
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film exhibits only weak crystallization despite its high boiling point.
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15 To assess the dependence on withdrawal speed of the crystallinities of the dip-coated
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17 films, the normalized UV-Vis absorption spectra of P3HT thin films processed from the
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19 Xyl/chlorinated solvent bi-phasic systems were compared (Figure S1). When P3HT molecules
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22 aggregate to form crystalline structures, vibronic bands appear at 558 and 608 nm that originate
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24 in the intermolecular electronic structure. The absorption spectra of the P3HT films processed
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26 from Xyl/CF contain a strongly pronounced (0−0) transition peak at 608 nm, which is one of the
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intermolecular vibronic bands and indicates the formation of well-ordered aggregates of P3HT
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31 chains.32 However, the (0-0) peak at 608 nm in the absorption spectra of the Xyl/CB-processed
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33 P3HT films has a slightly lower intensity. Furthermore, the (0-0) peak at 610 nm in the spectra of
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the Xyl/DCB-processed P3HT films is weak. The intensities of the vibronic peaks in the
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38 absorption spectra of all the processed films were found to be independent of the withdrawal
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40 speed.
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42 The lower energy bands in the absorption spectra provide information about the polymer
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45 chain conjugation length, which is associated with intramolecular and intermolecular ordering.
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47 Using Spano’s model and the assumption that the crystalline regions are composed of weakly
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49 interacting H-aggregates, the A0−0 and A0−1 vibronic bands can be fitted to calculate the free
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exciton bandwidth (W), which is related to the conjugation length of an individual polymer chain
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54 by the following equation,34
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  .⁄
4 ≈   .!"⁄
# (1)
 
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7 where A0−0 and A0−1 are the intensities of the (0−0) and (0−1) transitions respectively, and
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9 Ep is the vibrational energy of the symmetric vinyl stretch (assumed to be 180 meV). The W
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values calculated for the films dip-coated from Xyl/CF, Xyl/CB, and Xyl/DCB are compared in
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14 Figure 4b. The W values of the films processed with the Xyl/CF additive are constant (0.043 eV)
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16 regardless of the withdrawal speed. In contrast, the films processed from Xyl/CB and Xyl/DCB
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18 have lower W values, 0.052 eV and 0.061 eV respectively, than that of the Xyl/CF-processed
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21 film. These results indicate that the bi-phasic solvent with more mixing, i.e. Xyl/CF, induces the
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23 formation of P3HT with a longer conjugation length and stronger π−π interactions than the bi-
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25 phasic solvents containing CB and DCB.
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Atomic force microscopy (AFM) was used to determine the surface morphologies of the
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30 dip-coated P3HT thin films (Figure 4c). These three films were withdrawn from Xyl/CF, Xyl/CB,
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32 and Xyl/DCB at 5 mm/s. The AFM images clearly show that the Xyl/CF-processed P3HT film
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contains well-ordered thick nanowires with lengths of more than 300 nm whereas the films
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37 processed from Xyl/CB and Xyl/DCB contain smaller domains of crystalline lamellar packed
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39 phase. The fibrillar crystalline morphology of the Xyl/CF-processed film could result from
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41 solubility-mediated crystallization due to the poor solubility of P3HT in Xyl at room temperature.
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44 These results are in agreement with the UV-Vis results, which shows that the crystallization of
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46 P3HT in bi-phasic dip-coating processes is strongly affected by the mixing of the high-lying and
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48 low-lying solvents at the interface. Finally, the smallest difference in HSP solubility parameters
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arises for the Xyl/CF solvent pair, which results in the solubility-induced crystallization of P3HT,
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3 To determine how the dip-coating withdrawal speed affects the thickness of the P3HT
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thin films, the UV-vis absorption spectra and thickness of thin films dip-coated from the bi-
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8 phasic solutions with various withdrawal speeds were obtained (Figure 5). As the withdrawal
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10 speed increases from 1 to 10 mm/s, the overall intensity of the absorbance of the P3HT films
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increases. In particular, the intensity of the (0-1) peak at 580 nm increased from 0.3 to 0.8, which
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15 can be directly correlated with the thickness of the dip-coated film according to Lambert's law.
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17 The thickness of the dip-coated film can be determined by applying the Landau and Levich
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19 model for a steady state Newtonian fluid.35 When the substrate speed (typically in the range ~1–
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22 10 mm/s) and liquid viscosity η are low, the balance is modulated by the ratio of the viscous drag
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24 to the liquid-vapor surface tension γLV:
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/-
ℎ = 0.94(() )/" + ,
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(./)/ (2)
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29 where h0 is the thickness of the processed film, η is the liquid viscosity, U0 is the
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31 withdrawal speed, γLV is the liquid-vapor surface tension, ρ is the liquid density, and g is the
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acceleration due to gravity.
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36 The thickness, h0, was calculated from the UV-Vis results and plotted as a function of the
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38 withdrawal speed; the plot can be fitted with a power-law relation. The power exponent for the
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40 Xyl/CF-processed film is 0.669 for withdrawal speeds in the range 1 to 10 mm/s (Figure S2).
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43 According to equation (2), the power exponent is two thirds of the order of U0, which means that
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45 the Xyl/CF bi-phasic system maintains the draining mode at equilibrium, in which solvent
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47 evaporation and capillary feeding are balanced. However, the thicknesses of the films dip-coated
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from Xyl/CB and Xyl/DCB have weak dependences on the withdrawal speed. The power
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52 exponents of U0 for the Xyl/CB- and Xyl/DCB-processed films are 0.486 and 0.081 respectively.
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54 A possible reason for these results is that the evaporation rate of CB and DCB is too low to
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compensate for capillary feeding, which results in a transition from the draining mode to the
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3 capillary mode.36 In the capillary mode, solvent evaporation is slower than the movement of the
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drying line, which leads to continuous dragging from the meniscus by the precursor solution
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8 through capillary force. These results indicate that in bi-phasic solvent systems, the low-lying
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the relationship between film thickness and withdrawal speed.
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15 Optical microscopy (OM) images of the morphologies of the films dip-coated from the bi-
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17 phasic solutions after aging for various time intervals are presented in Figure 6. We confirmed
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19 that the color of the Xyl/CF solution changes from orange to dark brown, which means that the
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22 aggregation of P3HT increases with aging time. The film dip-coated from the Xyl/CF bi-phasic
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24 solution and aged for 1 min fully covers the substrate and has a smooth surface topology.
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26 However, when the aging time is longer than 3 min, the processed films contain precipitates of
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P3HT with sizes of the order of hundreds of micrometers that only barely achieve a uniform film
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31 coverage. In contrast, the films processed from the Xyl/CB and Xyl/DCB solutions have uniform
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33 and smooth film morphologies irrespective of the aging time. Thus strong P3HT aggregation in
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the bi-phasic solution state results in precipitates and non-homogeneous and rough surface
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38 morphologies. Therefore, to produce uniform and full-coverage thin films from the Xyl/CF bi-
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40 phasic solution, the dip-coating process must be carried out swiftly to reduce the solution aging
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42 time. The stable Xyl/CB and Xyl/DCB bi-phasic solution states produce smooth film
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45 morphologies over a broad range of aging times.
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47 To investigate the electrical characteristics of the P3HT films processed from bi-phasic
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49 solvents, the field-effect mobilities of the P3HT films were determined in OFETs with a top-
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contact geometry. Typical drain current (ID) versus gate voltage (VG) plots for OFETs operating
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54 in accumulation mode are shown in Figure 7. The on-current and field-effect mobility of the
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3 saturation at 7 mm/s (Table S1). This increase in the charge carrier mobility is attributed to the
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increase in the film thickness that results from an increase in withdrawal speed. The maximum
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8 mobility was measured to be 4.3 × 10-3 cm2V-1s-1. The results for the Xyl/CB-processed P3HT
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10 device are similar, with a maximum mobility of 3.3 × 10-3 cm2V-1s-1 at 10 mm s-1 (Table S2). The
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Xyl/DCB-processed device was found to exhibit the lowest mobility, 1.0 × 10-3 cm2V-1s-1, in the
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15 range 3 to 10 mm s-1 (Table S3). The trend in the field-effect mobilities is in agreement with that
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17 in the crystallinities of the P3HT films processed from the bi-phasic solvents, as confirmed by the
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19 UV−vis and AFM results. There is a small difference between the HSP values of the intermixed
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22 low-lying solvent CF and Xyl, so the bi-phasic system containing CF produces a film with
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24 enhanced crystallinity and nanowire formation, and high mobility. In contrast, there is a large
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26 difference between the HSP parameters of DCB and Xyl, so this bi-phasic system produces a film
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with low crystallinity and low mobility. Further, the variations in the electrical characteristics of
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31 the P3HT films were determined for various aging times and a withdrawal speed of 10 mm/s
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33 (Figure S3). The inset in Figure 7(d) shows that the Xyl/CF-processed P3HT film does not
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exhibit transistor performance for aging times longer than 3 min because severe P3HT
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38 aggregation occurs in the thin films (Figure 6). In the case of the Xyl/CF-processed P3HT films,
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40 the field-effect mobilities are maintained for all aging times, i.e. they provide reliable long-term
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42 stability (Table S4,5).
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45 Solubility parameters can be used to predict the compatibility of polymers with solvents.
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47 Liquids with similar solubility parameters are expected to be miscible, and polymers will dissolve
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49 in solvents with HSP values that are not too different from their own. The HSP is a measure of
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solubility and dispersivity and has been widely used in the analysis of the properties of polymers,
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The solubility parameter in its original
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δ = 12/3 (3)
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6 where u (J mol−1) is the molar cohesive energy and ν (cm3 mol−1) is the molar volume.
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8 Note that the closer the δ values of the solute and solvent species are to each other, the higher the
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solubility. The Hildebrand δ is inapplicable, however, to solutions with specific molecular
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13 interactions other than the dispersion force. Hansen thus divided the cohesive energy u into
14
15 contributions from the dispersion (D), polarity (P), and hydrogen-bonding (H) interactions, i.e. u
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17 = uD + uP + uH, to define the three-component solubility parameter (δD, δP, δH):
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20 δ = 12 /3, δ4 = 124 /3, δ6 = 126 /3 (4)
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22 These terms can be generalized according to Equations (3) and (4):
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25 δ = δ + δ4 + δ6
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27 In the 3D HSP space, the solubility can be characterized in terms of the modified distance
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Ra between the solvent and solute species:
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32 R 9 = 14(: − : ) + (:4 − :4 ) + (:6 − :6 ) (5)
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34
which differs from the normal distance because of the weighting factor 4 for the
35
36
37 dispersion component introduced by Hansen to account for the results of empirical testing. Note
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39 here that the shorter the solute−solvent distance Ra in the HSP space, the higher the solubility.
40
41 The solubility sphere method is commonly used for the determination of the HSP values of solid
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44 solutes from solubility data and also for the prediction of solubilities in other solvents. This
45
46 method is based on the principle that good solvents are located within a threshold radius R0 from
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48 the solute (Ra < R0), whereas poor solvents are located outside this radius (Ra > R0).
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Table 1 shows the differences between the HSP values of the solvents in the bi-phasic
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53 systems: that between Xyl and CF is the smallest, 0.9 MPa½, whereas that between Xyl and CB is
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55 1.5 MPa½, and the difference between the values of Xyl and DCB is 2.4 MPa½. We can then
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3 calculate the Ra values for the solvent pairs in HSP space, which increase in the following order:
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3.77 MPa½ (Xyl/CF), 4.25 MPa½ (Xyl/CB), and 6.47 MPa½ (Xyl/DCB). Thus the compatibility
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8 for intermixing is higher for Xyl and CF than for Xyl/CB and Xyl/DCB. These calculations
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10 provide insight into the bi-phasic separation behaviors of the high-lying P3HT:Xyl phases and
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the low-lying good solvent phases (Figure 8). To prepare each bi-phasic system, the marginal
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15 solvent Xyl dissolves P3HT at the temperature 90˚C, and this solution is added on top of the
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18 chlorinated good solvent with high density. Although the high-lying Xyl-P3HT phase and low-
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lying good solvent phase form a stable bi-phasic system, the molecular compatibility of the low-
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23 lying chlorinated good solvent and P3HT is high enough that solvents are exchanged at the
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25 interface. Therefore, near the interface the high-lying phase is expected to have three components,
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namely Xyl-good solvent-P3HT. The good solvent predominantly occupies the space near P3HT
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30 molecules in the solution state, which results in the formation of fully relaxed P3HT coils. If the
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32 intermixed good solvent has a small Ra value in its interactions with Xyl, the Xyl solvent
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34 molecules could influence P3HT molecular structure in solution state. As time goes by, P3HT
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37 aggregation proceeds further to produce preformed nanowire structures in solution. However, if
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39 the good solvent has a high Ra value with Xyl, the Xyl solvent molecules would be pushed away
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41 from the P3HT molecules due to the presence of the good solvent, which results in a stable
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solution without aggregation, as arises in the case of DCB/Xyl. Therefore, the differences
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46 between the HSP values of the high- and low-lying solvents in these bi-phasic systems are
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48 significant.
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We have systematically investigated the effects in bi-phasic dip-coating systems of the
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8 properties of the low-lying solvent on polymer aggregation and stability in the high-lying
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10 solution, on the resulting film morphology, and on device characteristics. We used HSP values to
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interpret how polymer aggregation and stability in the upper solution state develop as a function
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15 of aging time under the influence of the low-lying solvent. The compatibility of the high- and
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17 low-lying solvents determines the outcomes of solubility-induced P3HT aggregation, which
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19 affects the degree of P3HT crystallization and uniformity in the resulting thin films. The polymer
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22 crystallinity and film morphology are strongly correlated with the charge carrier mobility of field
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24 effect transistors. This bi-phasic dip-coating method has significant promise for the design and
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26 development of robust and effective organic electronic devices for a wide range of commercial
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applications.
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Supporting Information
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38 Table of device characteristics, UV-Vis absorption spectra, thickness value with withdrawal
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40 speed, and transfer curve for the P3HT thin films. This material is available free of charge via the
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42 Internet at http://pubs.acs.org.
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47 Acknowledgement
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49 This research was supported by Basic Science Research Program through the National Research
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Foundation of Korea (NRF) funded by the Ministry of Education (2016R1D1A1B03931906).
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3 References
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3 Figure Captions
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Figure 1. Photographs of bi-phasic systems with (a) a large difference between the densities of
7 the high- and low-lying solvents, and (b) a small difference between the densities of the two
8 solvents. (c) A schematic diagram of solvent intermixing at the interface of a bi-phasic system.
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10 Figure 2. Photographs of the bi-phasic systems Xyl/CF, Xyl/CB, and Xyl/DCB, and of Xyl, all
11 containing P3HT, after various aging times.
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14 Figure 3. (a) Photographs of pre-dissolved P3HT:Xyl solutions diluted with the chlorinated
15 solvents after various aging times. UV-Vis absorption spectra of dilute solutions of P3HT in (b)
16 Xyl/CF, (c) Xyl/CB, (d) Xyl/DCB, and (e) Xyl only.
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18 Figure 4. (a) Normalized UV-Vis absorption spectra of P3HT films dip-coated from the bi-
19 phasic solvents Xyl/CF, Xyl/CB, and Xyl/DCB. The inset shows the ratios of the intensities of
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the (0-0) and (0-2) peaks. (b) The ratio of the peak intensities of (0-0) and (0-1) as functions of
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22 the speeds of withdrawal of the dip-coated films from the bi-phasic systems. The inset shows the
23 variation in the exciton bandwidth (W) with the speed of withdrawal of the dip-coated films. (c)
24 Atomic force microscopy images of the P3HT films dip-coated from the bi-phasic solvents
25 Xyl/CF, Xyl/CB, and Xyl/DCB.
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27 Figure 5. UV-Vis absorption spectra of P3HT films dip-coated from the bi-phasic solvents (a)
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Xyl/CF, (b) Xyl/CB, and (c) Xyl/DCB for withdrawal speeds in the range 1 to 10 mm/s. (d) The
30 thicknesses of the P3HT films dip-coated from the bi-phasic systems for various withdrawal
31 speeds.
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33 Figure 6. Optical microscopy images of P3HT films dip-coated from the bi-phasic solvents
34 Xyl/CF, Xyl/CB, and Xyl/DCB for various aging times.
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37 Figure 7. Plots of the drain current versus the gate voltage at a fixed drain voltage of -80 V on
38 both linear (left axis) and log (right axis) scales for P3HT films dip-coated from the bi-phasic
39 solvents (a) Xyl/CF, (b) Xyl/CB, and (c) Xyl/DCB for various withdrawal speeds in the range 1
40 to 10 mm/s. (d) The variations with withdrawal speed in the average field-effect mobilities for
41 P3HT films dip-coated from the various bi-phasic solvents. The inset shows the variations in the
42 average field-effect mobilities with aging time.
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45 Figure 8. Schematic diagram of how HSP differences between two solvents affect their
46 intermixing in the bi-phasic system and polymer aggregation.
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3 Table 1. Physical properties and solubility parameters of P3HT and various solvents.
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6 Xylene Chloroform Chlorobenzene Dichlorobenzene
P3HT
7 (Xyl) (CF) (CB) (DCB)
8 Density (g/cm3) - 0.86 1.49 1.11 1.25
9
10 ∆δ (P3HT) - 1.9 1 0.4 0.5
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∆δ (XYL) 1.9 - 0.9 1.5 2.4
13 δ (MPa½) 20.0 18.1 19.0 19.6 20.5
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15 δd (MPa½) 18.5 17.9 17.8 19.0 19.2
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17 δp (MPa½) 5.3 0.7 3.1 4.3 6.6
18 δh (MPa½) 5.3 2.8 5.7 3.3 3.3
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20 Ra (XYL) 5.37 - 3.77 4.25 6.47
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22 Ra (P3HT) - 5.37 2.64 2.45 2.77
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B.P (℃) - 138 61 131 180
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60 ACS Paragon Plus Environment