10 1021@acs JPCC 7b11534

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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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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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a
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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The Journal of Physical Chemistry Page 2 of 29
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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:
7

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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56 film. These results indicate that the structure of a film dip-coated from a bi-phasic solvent is
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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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10 solvent significantly affects both evaporation and the capillary force, which critically determine
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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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56 Xyl/CF-processed P3HT film increase gradually as the withdrawal speed increases, and reach
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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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54 asphaltenes, pigments, and nanomaterials.31, 37-39
The solubility parameter in its original
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56 Hildebrand form δ is defined as the square root of the cohesive energy density:40
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58 12
59
1
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3
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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10
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
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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
26
27 In the 3D HSP space, the solubility can be characterized in terms of the modified distance
28
29
30
Ra between the solvent and solute species:
31
32 R 9 = 14(: − : ) + (:4 − :4 ) + (:6 − :6 ) (5)
33
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
38
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
42
43
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
47
48 the solute (Ra < R0), whereas poor solvents are located outside this radius (Ra > R0).
49
50
51
Table 1 shows the differences between the HSP values of the solvents in the bi-phasic
52
53 systems: that between Xyl and CF is the smallest, 0.9 MPa½, whereas that between Xyl and CB is
54
55 1.5 MPa½, and the difference between the values of Xyl and DCB is 2.4 MPa½. We can then
56
57
58 13
59
1
2
3 calculate the Ra values for the solvent pairs in HSP space, which increase in the following order:
4
5
6
3.77 MPa½ (Xyl/CF), 4.25 MPa½ (Xyl/CB), and 6.47 MPa½ (Xyl/DCB). Thus the compatibility
7
8 for intermixing is higher for Xyl and CF than for Xyl/CB and Xyl/DCB. These calculations
9
10 provide insight into the bi-phasic separation behaviors of the high-lying P3HT:Xyl phases and
11
12
the low-lying good solvent phases (Figure 8). To prepare each bi-phasic system, the marginal
13
14
15 solvent Xyl dissolves P3HT at the temperature 90˚C, and this solution is added on top of the
16
17
18 chlorinated good solvent with high density. Although the high-lying Xyl-P3HT phase and low-
19
20
21
lying good solvent phase form a stable bi-phasic system, the molecular compatibility of the low-
22
23 lying chlorinated good solvent and P3HT is high enough that solvents are exchanged at the
24
25 interface. Therefore, near the interface the high-lying phase is expected to have three components,
26
27
namely Xyl-good solvent-P3HT. The good solvent predominantly occupies the space near P3HT
28
29
30 molecules in the solution state, which results in the formation of fully relaxed P3HT coils. If the
31
32 intermixed good solvent has a small Ra value in its interactions with Xyl, the Xyl solvent
33
34 molecules could influence P3HT molecular structure in solution state. As time goes by, P3HT
35
36
37 aggregation proceeds further to produce preformed nanowire structures in solution. However, if
38
39 the good solvent has a high Ra value with Xyl, the Xyl solvent molecules would be pushed away
40
41 from the P3HT molecules due to the presence of the good solvent, which results in a stable
42
43
44
solution without aggregation, as arises in the case of DCB/Xyl. Therefore, the differences
45
46 between the HSP values of the high- and low-lying solvents in these bi-phasic systems are
47
48 significant.
49
50
51
52
53
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58 14
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1
2
3 Conclusions
4
5
6
We have systematically investigated the effects in bi-phasic dip-coating systems of the
7
8 properties of the low-lying solvent on polymer aggregation and stability in the high-lying
9
10 solution, on the resulting film morphology, and on device characteristics. We used HSP values to
11
12
interpret how polymer aggregation and stability in the upper solution state develop as a function
13
14
15 of aging time under the influence of the low-lying solvent. The compatibility of the high- and
16
17 low-lying solvents determines the outcomes of solubility-induced P3HT aggregation, which
18
19 affects the degree of P3HT crystallization and uniformity in the resulting thin films. The polymer
20
21
22 crystallinity and film morphology are strongly correlated with the charge carrier mobility of field
23
24 effect transistors. This bi-phasic dip-coating method has significant promise for the design and
25
26 development of robust and effective organic electronic devices for a wide range of commercial
27
28
29
applications.
30
31
32
33
34
35
Supporting Information
36
37
38 Table of device characteristics, UV-Vis absorption spectra, thickness value with withdrawal
39
40 speed, and transfer curve for the P3HT thin films. This material is available free of charge via the
41
42 Internet at http://pubs.acs.org.
43
44
45
46
47 Acknowledgement
48
49 This research was supported by Basic Science Research Program through the National Research
50
51
52
Foundation of Korea (NRF) funded by the Ministry of Education (2016R1D1A1B03931906).
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58 15
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1
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3 References
4 (1) Heremans, P.; Tripathi, A. K.; de Jamblinne de Meux, A.; Smits, E. C. P.; Hou, B.; Pourtois,
5
6
G.; Gelinck, G. H. Mechanical and Electronic Properties of Thin-Film Transistors on Plastic, and
7 Their Integration in Flexible Electronic Applications. Adv. Mater. 2016, 28, 4266-4282.
8 (2) Mandal, S.; Noh, Y.-Y. Printed Organic Thin-Film Transistor-Based Integrated Circuits.
9 Semicond. Sci. Technol. 2015, 30, 064003.
10 (3) Forrest, S. R. The Path to Ubiquitous and Low-Cost Organic Electronic Appliances on Plastic.
11 Nature 2004, 428, 911-918.
12
(4) Arias, A. C.; MacKenzie, J. D.; McCulloch, I.; Rivnay, J.; Salleo, A. Materials and
13
14 Applications for Large Area Electronics: Solution-Based Approaches. Chem. Rev. 2010, 110, 3-
15 24.
16 (5) Dimitrakopoulos, C. D.; Malenfant, P. R. L. Organic Thin Film Transistors for Large Area
17 Electronics. Adv. Mater. 2002, 14, 99-117.
18 (6) Wang, W.; Wang, L.; Dai, G.; Deng, W.; Zhang, X.; Jie, J.; Zhang, X. Controlled Growth of
19 Large-Area Aligned Single-Crystalline Organic Nanoribbon Arrays for Transistors and Light-
20
Emitting Diodes Driving. Nano-Micro Lett. 2017, 9, 52.
21
22 (7) Yan, H.; Chen, Z.; Zheng, Y.; Newman, C.; Quinn, J. R.; Dotz, F.; Kastler, M.; Facchetti, A.
23 A High-Mobility Electron-Transporting Polymer for Printed Transistors. Nature 2009, 457, 679-
24 686.
25 (8) Bharti, D.; Raghuwanshi, V.; Varun, I.; Mahato, A. K.; Tiwari, S. P. Directional Solvent
26 Vapor Annealing for Crystal Alignment in Solution-Processed Organic Semiconductors. ACS
27 Appl. Mater. Interfaces 2017, 9, 26226-26233.
28
29
(9) Zhang, Y.; Jie, J.; Sun, Y.; Jeon, S.-G.; Zhang, X.; Dai, G.; Lee, C. J.; Zhang, X. Precise
30 Patterning of Organic Single Crystals via Capillary-Assisted Alternating-Electric Field. Small
31 2017, 13, 1604261.
32 (10) Zhang, Z.; Peng, B.; Ji, X.; Pei, K.; Chan, P. K. L. Marangoni-Effect-Assisted Bar-Coating
33 Method for High-Quality Organic Crystals with Compressive and Tensile Strains. Adv. Funct.
34 Mater. 2017, 27, 1703443.
35
(11) Faustini, M.; Louis, B.; Albouy, P. A.; Kuemmel, M.; Grosso, D. Preparation of Sol−Gel
36
37 Films by Dip-Coating in Extreme Conditions. J. Phys. Chem. C 2010, 114, 7637-7645.
38 (12) Tang, X.; Yan, X. Dip-Coating for Fibrous Materials: Mechanism, Methods and
39 Applications. J. Sol-Gel Sci. Technol. 2017, 81, 378-404.
40 (13) Wang, B.; Zhu, T.; Huang, L.; Tam, T. L. D.; Cui, Z.; Ding, J.; Chi, L. Addressable Growth
41 of Oriented Organic Semiconductor Ultra-Thin Films on Hydrophobic Surface by Direct Dip-
42 Coating. Org. Electron. 2015, 24, 170-175.
43
(14) Wu, K.; Li, H.; Li, L.; Zhang, S.; Chen, X.; Xu, Z.; Zhang, X.; Hu, W.; Chi, L.; Gao, X. et al.
44
45 Controlled Growth of Ultrathin Film of Organic Semiconductors by Balancing the Competitive
46 Processes in Dip-Coating for Organic Transistors. Langmuir 2016, 32, 6246-6254.
47 (15) Wang, G.; Hirasa, T.; Moses, D.; Heeger, A. J. Fabrication of Regioregular Poly(3-
48 hexylthiophene) Field-Effect Transistors by Dip-Coating. Synth. Met. 2004, 146, 127-132.
49 (16) Li, L.; Gao, P.; Wang, W.; Müllen, K.; Fuchs, H.; Chi, L. Growth of Ultrathin Organic
50 Semiconductor Microstripes with Thickness Control in the Monolayer Precision. Angew. Chem.
51
52
Int. Ed. 2013, 52, 12530-12535.
53 (17) Jang, J.; Nam, S.; Im, K.; Hur, J.; Cha, S. N.; Kim, J.; Son, H. B.; Suh, H.; Loth, M. A.;
54 Anthony, J. E. et al. Highly Crystalline Soluble Acene Crystal Arrays for Organic Transistors:
55 Mechanism of Crystal Growth During Dip-Coating. Adv. Funct. Mater. 2012, 22, 1005-1014.
56
57
58 16
59
1
2
3 (18) Mori, T.; Oyama, T.; Komiyama, H.; Yasuda, T. Solution-Grown Unidirectionally Oriented
4 Crystalline Thin Films of a U-Shaped Thienoacene-Based Semiconductor for High-Performance
5
6
Organic Field-Effect Transistors. J. Mater. Chem. C 2017, 5, 5872-5876.
7 (19) Ceratti, D. R.; Louis, B.; Paquez, X.; Faustini, M.; Grosso, D. A New Dip Coating Method
8 to Obtain Large-Surface Coatings with a Minimum of Solution. Adv. Mater. 2015, 27, 4958-4962.
9 (20) Kim, Y.-J.; Jung, H.-T.; Ahn, C. W.; Jeon, H.-J. Simultaneously Induced Self-Assembly of
10 Poly(3-hexylthiophene) (P3HT) Nanowires and Thin-Film Fabrication via Solution-Floating
11 Method on a Water Substrate. Adv. Mater. Interfaces 2017, 4, 1700342.
12
(21) Li, M.; An, C.; Pisula, W.; Müllen, K. Alignment of Organic Semiconductor Microstripes by
13
14 Two-Phase Dip-Coating. Small 2014, 10, 1926-1931.
15 (22) Park, Y. D.; Lee, H. S.; Choi, Y. J.; Kwak, D.; Cho, J. H.; Lee, S.; Cho, K. Solubility-
16 Induced Ordered Polythiophene Precursors for High-Performance Organic Thin-Film Transistors.
17 Adv. Funct. Mater. 2009, 19, 1200-1206.
18 (23) Oh, S.; Yang, M.; Bouffard, J.; Hong, S.; Park, S.-J. Air–Liquid Interfacial Self-Assembly of
19 Non-Amphiphilic Poly(3-hexylthiophene) Homopolymers. ACS Appl. Mater. Interfaces 2017, 9,
20
12865-12871.
21
22 (24) Opoku, H.; Nketia-Yawson, B.; Shin, E. S.; Noh, Y.-Y. Controlling Organization of
23 Conjugated Polymer Films from Binary Solvent Mixtures for High Performance Organic Field-
24 Effect Transistors. Org. Electron. 2017, 41, 198-204.
25 (25) Corrales, T. P.; Bai, M.; del Campo, V.; Homm, P.; Ferrari, P.; Diama, A.; Wagner, C.; Taub,
26 H.; Knorr, K.; Deutsch, M. et al. Spontaneous Formation of Nanopatterns in Velocity-Dependent
27 Dip-Coated Organic Films: From Dragonflies to Stripes. ACS Nano 2014, 8, 9954-9963.
28
29
(26) Zhu, T.; Xiao, C.; Wang, B.; Hu, X.; Wang, Z.; Fan, J.; Huang, L.; Yan, D.; Chi, L. Growth
30 of Highly Oriented Ultrathin Crystalline Organic Microstripes: Effect of Alkyl Chain Length.
31 Langmuir 2016, 32, 9109-9117.
32 (27) Reichardt, C.; Welton, T. Solvents and Solvent Effects in Organic Chemistry, 3rd ed., Wiley-
33 VCH Publishers: 2003.
34 (28) Xue, L.; Yu, X.; Han, Y. Different Structures and Crystallinities of Poly(3-hexylthiophene)
35
Films Prepared from Aged Solutions. Colloids Surf. A 2011, 380, 334-340.
36
37 (29) Fu, C.-M.; Jeng, K.-S.; Li, Y.-H.; Hsu, Y.-C.; Chi, M.-H.; Jian, W.-B.; Chen, J.-T. Effects of
38 Thermal Annealing and Solvent Annealing on the Morphologies and Properties of Poly(3-
39 hexylthiophene) Nanowires. Macromol. Chem. Phys. 2015, 216, 59-68.
40 (30) Hu, H.; Zhao, K.; Fernandes, N.; Boufflet, P.; Bannock, J. H.; Yu, L.; de Mello, J. C.;
41 Stingelin, N.; Heeney, M.; Giannelis, E. P. et al. Entanglements in Marginal Solutions: a Means
42 of Tuning Pre-Aggregation of Conjugated Polymers with Positive Implications for Charge
43
Transport. J. Mater. Chem. C 2015, 3, 7394-7404.
44
45 (31) Hansen, C. M.; Smith, A. L. Using Hansen Solubility Parameters to Correlate Solubility of
46 C60 Fullerene in Organic Solvents and in Polymers. Carbon 2004, 42, 1591-1597.
47 (32) Brown, P. J.; Thomas, D. S.; Köhler, A.; Wilson, J. S.; Kim, J. S.; Ramsdale, C. M.;
48 Sirringhaus, H.; Friend, R. H. Effect of Interchain Interactions on the Absorption and Emission of
49 Poly(3-hexylthiophene). Phys. Rev. B: Condens. Matter Mater. Phys. 2003, 67, 642031-6420316.
50 (33) Urien, M.; Bailly, L.; Vignau, L.; Cloutet, E.; de Cuendias, A.; Wantz, G.; Cramail, H.;
51
52
Hirsch, L.; Parneix, J.-P. Effect of the Regioregularity of Poly(3-hexylthiophene) on the
53 Performances of Organic Photovoltaic Devices. Polym. Int. 2008, 57, 764-769.
54 (34) Clark, J.; Silva, C.; Friend, R. H.; Spano, F. C. Role of Intermolecular Coupling in the
55 Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular
56 Polythiophene. Phys. Rev. Lett. 2007, 98, 206406.
57
58 17
59
1
2
3 (35) Landau, L.; Levich, B. Dragging of a Liquid by a Moving Plate. Acta Physicochimica
4 U.R.S.S. 1942, 17, 42-54.
5
6
(36) Bindini, E.; Naudin, G.; Faustini, M.; Grosso, D.; Boissière, C. Critical Role of the
7 Atmosphere in Dip-Coating Process. J. Phys. Chem. C 2017, 121, 14572-14580.
8 (37) Hansen, C. M. Hansen Solubility Parameters - A User's Handbook, 2nd edition, CRC Press:
9 Boca Raton, 2007.
10 (38) Machui, F.; Abbott, S.; Waller, D.; Koppe, M.; Brabec, C. J. Determination of Solubility
11 Parameters for Organic Semiconductor Formulations. Macromol. Chem. Phys. 2011, 212, 2159-
12
2165.
13
14 (39) Takebayashi, Y.; Morii, N.; Sue, K.; Furuya, T.; Yoda, S.; Ikemizu, D.; Taka, H. Solubility
15 of N,N′-Di(1-naphthyl)-N,N′-diphenyl Benzidine (NPB) in Various Organic Solvents:
16 Measurement and Correlation with the Hansen Solubility Parameter. Ind. Eng. Chem. Res. 2015,
17 54, 8801-8808.
18 (40) Hildebrand, J. H.; Scott, R. L. The Entropy of Solution of Nonelectrolytes. J. Chem. Phys.
19 1952, 20, 1520-1521.
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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.
9
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.
12
13
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.
17
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
20
the (0-0) and (0-2) peaks. (b) The ratio of the peak intensities of (0-0) and (0-1) as functions of
21
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.
26
27 Figure 5. UV-Vis absorption spectra of P3HT films dip-coated from the bi-phasic solvents (a)
28
29
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.
32
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.
35
36
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.
43
44
45 Figure 8. Schematic diagram of how HSP differences between two solvents affect their
46 intermixing in the bi-phasic system and polymer aggregation.
47
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58 19
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1
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3 Table 1. Physical properties and solubility parameters of P3HT and various solvents.
4
5
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
11
12
∆δ (XYL) 1.9 - 0.9 1.5 2.4
13 δ (MPa½) 20.0 18.1 19.0 19.6 20.5
14
15 δd (MPa½) 18.5 17.9 17.8 19.0 19.2
16
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
19
20 Ra (XYL) 5.37 - 3.77 4.25 6.47
21
22 Ra (P3HT) - 5.37 2.64 2.45 2.77
23
B.P (℃) - 138 61 131 180
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