Browsing by Author "Su, Chun-Jen"

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Bispentafluorophenyl-Containing Additive: Enhancing Efficiency and Morphological Stability of Polymer Solar Cells via Hand-Grabbing-Like Supramolecular Pentafluorophenyl-Fullerene Interactions
(2017-12-20)
Hung, Kai-En
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Tsai, Che-En
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Chang, Shao-Ling
;
Lai, Yu-Ying
;
Jeng, U-Ser
A new class of additive materials bis(pentafluorophenyl) diesters (BFEs) where the two pentafluorophenyl (C6F5) moieties are attached at the both ends of a linear aliphatic chain with tunable tether lengths (BFS, BF7, and BF13) were designed and synthesized. In the presence of BF7 to restrict the migration of fullerehe by hand-grabbing-like supramolecular interactions induced between the C6F5 groups and the surface of fullerene, the P3HT:PC61BM:BF7 device showed stable device characteristiCs after thermal heating at 150 degrees C for 25, 'IL The morphologies Of the active layers were systematically investigated by optical microscopy, grazing-incidence small-angle X-ray scattering (GISAXS), and atomic force microscopy. The tether length between the two C6F5 groups plays a pivotal role in controlling the intermolecular attractions. BF13 with a long and flexible tether might form a BF13-fullerene sandwich complex that fails to prevent fullerene's movement and aggregation, while BF5 with too short tether length decreases the possibility of interactions between the C6F5 groups and the fullerenes. BF7 with the optimal tether length has the best ability to stabilize the morphology. In sharp contrast, the nonfluorinated BP7 analogue without C6F5-C-60 physical interactions does not have the capability of morphological stabilization, unambiguously revealing the necessity of the C6F5 group. Most importantly, the function of BF7 can be also applied to the high-performance PffBT4BT-20D:PC71BM system, which exhibited an original PCE of 8.80%. After thermal heating at 85 degrees C for 200 h, the efficiency of the Pffi3T4BT-20D:PC71BM:BF7 device only decreased slightly to 7.73%, maintaining 88% of its original efficiency. To the best of our knowledge, this is the first time that the thermabdriven morphological evolution of the high-performance PffBT4BT-20D polymer has been investigated, and its morphological stability in the inverted device can be successfully preserved by the incorporation of BF7. This research also demonstrates that BF7 is not only effective with PC61BM but also to PC71BM.
Competition between Fullerene Aggregation and Poly(3-hexylthiophene) Crystallization upon Annealing of Bulk Heterojunction Solar Cells
(2011-08-01)
Wu, Wei-Ru
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Jeng, U-Ser
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Su, Chun-Jen
;
Wei, Kung-Hwa
;
Su, Ming-Shin
Concomitant development of [6,6]-phen-C(61)-butyric acid methyl ester (PCBM) aggregation and poly(3-hexylthiophene) (P3HT) crystallization in bulk heterojunction (BHJ) thin-film (ca. 85 nm) solar cells has been revealed using simultaneous grazing incidence small-/wide-angle X-ray scattering (GISAXS/GIWAXS). With enhanced time and spatial resolutions (5 s/frame; minimum q approximate to 0.004 angstrom(-1)), synchrotron GISAXS has captured In detail the fast growth in size of PCBM aggregates from 7 to 18 nm within 100 s of annealing at 150 degrees C. Simultaneously observed is the enhanced crystallization of P3HT Into lamellae oriented mainly perpendicular but also parallel to the substrate. An Avrami analysis of the observed structural evolution indicates that the faster PCBM aggregation follows a diffusion-controlled growth process (confined by P3HT segmental motion), whereas-the slower development of crystalline P3HT nanograins is characterized by constant nucleation rate (determined by the degree. of supercooling and POW demixing). These two competing kinetics result in local phase separation with space filling PCBM and P3HT nanodomains less than 20 nm in size when annealing temperature is kept below 180 degrees C. Accompanying the morphological development is the synchronized Increase In electron and hole mobilities of the BHJ thin-film solar cells, revealing the sensitivity of the carrier transport of the device on the structural features of PCBM and P3HT nanodomains. Optimized structural parameters, including the aggregate size and mean spacing of the PCBM aggregates, are quantitatively correlated to the device performance; a comprehensive network structure of the optimized BHJ thin film is presented.
Competition between PCBM Aggregation and P3HT crystallization in thin films upon annealing
(2011-01-01)
Jeng, U-Ser
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Wu, Wei-Ru
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Su, Chun-Jen
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Wei, Kung-Hwa
;
Su, Ming-Shin
Complementary solvent additives tune the orientation of polymer lamellae, reduce the sizes of aggregated fullerene domains, and enhance the performance of bulk heterojunction solar cells
(2014-01-01)
Liu, Chih-Ming
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Su, Yu-Wei
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Jiang, Jian-Ming
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Chen, Hsiu-Cheng
;
Lin, Shu-Wei
In this study we employed 1-chloronaphthalene (CN) and 1,8-diiodooctane (DIO) as binary additives exhibiting complementarily preferential solubility for processing the crystalline conjugated polymer poly[bis(dodecyl)thiophene-dodecyl-thieno[3,4-c]pyrrole-4,6-dione] (PBTC12TPD) and the fullerene [6,6]-phenyl-C-71-butyric acid methyl ester (PC71BM) in chloroform. Using synchrotron grazing-incidence small-/wide-angle X-ray scattering and transmission electron microscopy to analyse the structure of the PBTC12TPD-PC71BM blend films, we found that the binary additives with different volume ratios in the processing solvent allow us to tune the relative population of face-on to edge-on PBTC12TPD lamellae and the size of PC71BM clusters in the blend films; the sizes of the fractal-like PC71BM clusters and the aggregated domains of PC71BM clusters increased and decreased, respectively, upon increasing the amount of DIO, whereas the relative ratio of face-on to edge-on PBTC12TPD lamellae increased upon increasing the amount of CN. When fabricating the photovoltaic devices, the short-circuit current density of the devices with the PBTC12TPD-PC71BM active layer having been processed with the binary additives is higher than that of the device incorporating an active layer processed without any additive. As a result, the power conversion efficiency of a device incorporating an active layer of PBTC12TPD-PC71BM (1 : 1.5, w/w) processed with binary additives of 0.5% DIO and 1% CN in chloroform increased to 6.8% from a value of 4.9%, a relative increase of 40%, for the corresponding device containing the same active layer but processed without any additive.
Distribution of Crystalline Polymer and Fullerene Clusters in Both Horizontal and Vertical Directions of High-Efficiency Bulk Heterojunction Solar Cells
(2013-06-26)
Liu, Chih-Ming
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Su, Ming-Shin
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Jiang, Jian-Ming
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Su, Yu-Wei
;
Su, Chun-Jen
In this study, we used (i) synchrotron grazing-incidence small-/wide-angle X-ray scattering to elucidate the crystallinity of the polymer PBTC12TPD and the sizes of the clusters of the fullerenes PC61BM and ThC61BM and (ii) transmission electron microscopy/electron energy loss spectroscopy to decipher both horizontal and vertical distributions of fullerenes in PBTC12TPD/fullerene films processed with chloroform, chlorobenzene and dichlorobezene. We found that the crystallinity of the polymer and the sizes along with the distributions of the fullerene clusters were critically dependent on the solubility of the polymer in the processing solvent when the solubility of fullerenes is much higher than that of the polymer in the solvent. In particular, with chloroform (CF) as the processing solvent, the polymer and fullerene units in the PBTC12TPD/ThC61BM layer not only give rise to higher crystallinity and a more uniform and finer fullerene cluster dispersion but also formed nanometer scale interpenetrating network structures and presented a gradient in the distribution of the fullerene clusters and polymer, with a higher polymer density near the anode and a higher fullerene density near the cathode. As a result of combined contributions from the enhanced polymer crystallinity, finer and more uniform fullerene dispersion and gradient distributions, both the short current density and the fill factor for the device incorporating the CF-processed active layer increase substantially over that of the device incorporating a dichlorobenzene-processed active layer; the resulting power conversion efficiency of the device incorporating the CF-processed active layer was enhanced by 46% relative to that of the device incorporating a dichlorobenzene-processed active layer.
Effect of Porogen Incorporation on Pore Morphology of Low-k SiCxNy Films Prepared Using PECVD
(2015-01-01)
Tu, Hung-En
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Su, Chun-Jen
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Jeng, U-Ser
;
Leu, Jihperng
;
材料科學與工程學系
Low-k porous SiCxNy films were prepared through plasma-enhanced chemical vapor deposition, using 1,3,5-trimethyl-1,3,5-trivinylcyclotrisilazane (VSZ) as the matrix precursor and epoxycyclohexane (ECH) as a porogen. The effects of porogen loading and deposition temperature on porogen incorporation, pore morphology, and the properties of porous SiCxNy films were examined. In addition, the impact of film shrinkage and the corresponding nanopore structures after annealing were studied. The porosity of films deposited at 100 degrees C increased from 1.8% to 19.8% when ECH loading increased to 30%, above which the porosity remained nearly constant because of high film shrinkage. The pore size decreased slightly from 4.1 to 3.7 nm when ECH loading increased to 30%, above which the pores became larger and were broadly distributed. By contrast, increasing deposition temperature at 20% ECH loading decreased porogen incorporation and increased film density. The porosities and pore size of films decreased, respectively, when the deposition temperature increased. A short-range ordering of pores was observed only at low deposition temperatures because the N-Si-C cross-linked structures and organic phase were present. Optimized processing parameters facilitated the fabrication of low-k porous SiCxNy films exhibiting 19.8% porosity, 3.7-nm pores, a k value of 3.18, and an elastic modulus of 7.7 GPa. (C) The Author(s) 2014. Published by ECS. All rights reserved.
Improving Device Efficiency of Polymer/Fullerene Bulk Heterojunction Solar Cells Through Enhanced Crystallinity and Reduced Grain Boundaries Induced by Solvent Additives
(2011-08-02)
Su, Ming-Shin
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Kuo, Chih-Yin
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Yuan, Mao-Chuan
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Jeng, U-Ser
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Su, Chun-Jen
The power conversion efficiency of a device incorporating a crystalline polymer/fullerene thin film improves from 5% to 7.3% - a relative increase of 45% - when an additive, diiodohexane (DIH), is present during processing. The DIH-processed active layer exhibits substantially enhanced polymer crystallinity and smaller fractal-like fullerene clusters.
Intrinsic coordination for revealing local structural changes in protein folding-unfolding
(2016-01-28)
Shiu, Ying-Jen
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Hayashi, Michitoshi
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Shih, Orion
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Su, Charlene
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Tsai, Min-Yeh
With a deformed object of a rigid rod inside, the local dislocations may be tracked relatively easily with respect to the internal rigid rod. We apply this concept on protein folding-unfolding to track the internal structural changes of an unfolded protein in solution. Proposed here is a protein internal coordination based on the major axis X of an ellipsoidal protein and the stable intrinsic transition dipole moment mu of the protein during unfolding. In this methodology, small-angle X-ray scattering (SAXS) is used to provide the protein global morphologies in the native and unfolded states. Furthermore, time-resolved fluorescence anisotropy (TRFA) provides the relative orientation between X and mu of Trp59 of the model protein cytochrome c. Hence observed in the protein unfolding with denaturants, acid, urea, or GuHCl, is the elongation of the native protein conformation along a reoriented protein major axis; accompanied are the different extents of relocations of the terminal a helices and loop structures of the protein in the corresponding unfolding.
Mesostructured Arrays of Nanometer-spaced Gold Nanoparticles for Ultrahigh Number Density of SERS Hot Spots
(2014-05-01)
Lai, Ying-Huang
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Chen, Shiaw-Woei
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Hayashi, Michitoshi
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Shiu, Ying-Jen
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Huang, Chiao-Cheng
A novel one-trough synthesis via an air-water interface is demonstrated to provide hexagonally packed arrays of densely spaced metallic nanoparticles (NPs). In the synthesis, a mesostructured polyoxometalate (POM)-silicatropic template (PSS) is first self-assembled at the air-water interface; upon UV irradiation, anion exchange cycles enable the free-floating PSS film to continuously uptake gold precursors from the solution subphase for diffusion-controlled and POM-site-directed photoreduction inside the silica channels. NPs approximate to 2 nm can hence be homogeneously formed inside the silica-surfactant channels until saturation. As revealed via X-ray diffraction, small-angle X-ray scattering (SAXS), grazing incidence SAXS, and transmission electron microscopy, the Au NPs directed by the PSS template are arrayed into a 2D hexagonal lattice with inter-channel spacing of 3.2 nm and a mean along-channel NP spacing of 2.8 nm. This corresponds to an ultra-high number density (approximate to 10(19) NPs cm(-3)) of narrowly spaced Au NPs in the Au-NP@PSS composite, leading to 3D densely deployed hot-spots along and across the mesostructured POM-silica channels for surface-enhanced Raman scattering (SERS). Consequently, the Au-NP@PSS composite exhibits prominent SERS with 4-mercaptobenzoic acid (4-MBA) adsorbed onto Au NPs. The best 4-MBA detection limit is 5 nm, with corresponding SERS enhancement factors above 10(8).
Multi-scale mapping for collagen-regulated mineralization in bone remodeling of additive manufacturing porous implants
(2019-05-15)
Tsai, Pei-I.
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Lam, Tu-Ngoc
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Wu, Meng-Huang
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Tseng, Kuan-Ying
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Chang, Yuan-Wei
Long term success of metallic fusion cages depends on mechanobiological processes through the bone incorporation and rich osseointegration. An optimal configuration of porous titanium-aluminum-vanadium (Ti-6Al-4V) implant fabricated via the additive manufacturing was evaluated in complimentary structure examinations to investigate the growth of autologous osseous at multi-length scales. X-ray microcomputed tomography (micro-CT) and transmission X-ray microscopy (TXM) using newly-built analysis method indicate the porous Ti-6Al-4V is much better for bone ingrowth compared to commercially non-porous titanium (Ti) and porous tantalum (Ta) implants at the ultramicrostructural level. The evolution of bone formation and remodeling acquired by nano X-ray Laue diffraction mapping exhibits the isotropic orientation and low crystallinity of all newly formed bone whereas mature bone in Ti-6Al-4V discloses the preferential alignment and higher crystallinity volumes of constituent hydroxyapatite (HA) crystallites. The high degree in mineral crystallinity of the fully mature bone suggests additive manufactured Ti-6Al-4V pores enhance the collagen-regulated mineralization.
On Modulating the Phase Behavior of Block Copolymer/Homopolymer Blends via Hydrogen Bonding
(2010-01-26)
Chen, Shih-Chien
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Kuo, Shiao-Wei
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Jeng, U-Ser
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Su, Chun-Jen
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Chang, Feng-Chih
We have investigated the phase behavior or poly(4-vinylphenol-b-styrene) (PVPh-b-PS) when respectively blended with poly(4-vinylpyridine) (NVP), poly(methyl methacrylate) (PMMA), and PVPh homopolymers by mediated hydrogen bonding strengths with the PVPh block of the copolymer. The Fourier transform infrared spectroscopic result indicates that the PVPh-b-PS/P4VP blend has a much higher fraction (f(H)) of hydrogen-bonded PVPh blocks for it significantly higher miscibility compared with the blends with PMMA and PVPh homopolymers. Consequently, the PVPh-b-PS/P4VP blend, behaving as a neat diblock copolymer, exhibited a series of order-order phase transitions from the lamellar, gyroid, hexagonally packed cylinder to body-centered cubic structures when the P4VP content increases from 6 to 71% (volume fraction), as evidenced consistently by transmission electron microscopy and small-angle X-ray scattering. In contrast, both file PVPh-b-PS/PMMA and PVPh-b-PS/PVPh blends maintained essentially the lamellar structure upon a similar volume fraction increase in the homopolymers; the lamellar structure, however, was distorted to different extents at higher volume fractions of the additives, depending on the hydrogen bonding strength. On the basis of the results, the ratio of interassociation equilibrium constant (KA) over self-association equilibrium constant (K(B)), K(A)/K(B), is introduced as a convenient guide in estimating the phase behavior of similar polymer blends featuring hydrogen bonding interactions between file homopolymer additive and copolymer: with a K(A)/K(B) ratio much larger than unity, the blend system tends to behave as a neat copolymer; with a K(A)/K(B) ratio significantly smaller than unity, phase separation instead of order-order phase transitions call be expected for the blend above certain volume fraction of homopolymer additive.
Pore morphology of low-k SiCxNy films prepared with a cyclic silazane precursor using plasma-enhanced chemical vapor deposition
(2015-09-01)
Tu, Hung-En
;
Su, Chun-Jen
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Jeng, U-Ser
;
Leu, Jihperng
;
材料科學與工程學系
Low-k SiCxNy films were prepared using radio-frequency plasma-enhanced chemical vapor deposition (PECVD), with only 1,3,5-trimethyl-1,3,5-trivinylcyclotrisilazane (VSZ) as the precursor; VSZ has cyclic Si-N-Si linkages and three pendent vinyl groups. At lower PECVD temperatures, SiCxNy films possess relatively low film densities, indicating the existence of a loose structure or voidswithin the cross-linked matrix structure. The poremorphology of SiCxNy films deposited at distinct temperatures were examined using grazing-incidence small-angle X-ray scattering, while the chemical bondings and structural information were analyzed using Fourier-transform infrared spectroscopy. At 100 degrees C, SiCxNy films without porogen displaying 4.9 nm pores and a mean pore spacing of 30.1nmgenerated low-density films because Si-(CH2)(n)-Si and/or Si-(CH2)(n)-CH3 could be incorporated free volume into the N-Si-C cross-linked structure under plasma deposition. At 300 degrees C, the N-Si-C cross-linked structure and the some organic phase were disrupted and transformed into a denser structure, reducing pore size (3.5 nm) and losing pore correlation. Thus, low deposition temperatures facilitate the formation of large pores and the ordering of the pores. Post annealing converted the 100 and 300 degrees C as-deposited SiCxNy films into loose and dense structures, respectively, and maintained slightly reduced pore size and pore correlation in the annealed films. (C) 2015 Elsevier B.V. All rights reserved.
Quantitative Characterization and Mechanism of Formation of Multilength-scale Bulk Heterojunction Structures in Highly Efficient Solution-Processed Small-Molecule Organic Solar Cells
(2015-07-23)
Huang, Yu-Ching
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Tsao, Cheng-Si
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Huang, Tzu-Yen
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Cha, Hou-Chin
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Patra, Dhananjaya
In this study we used simultaneous grazing-incidence small- and wide-angle X-ray scattering (GISAXS and GIWAXS, respectively) to probe the multilength-scale structures of thin active layers comprising the linear A-D-A-type pi-conjugated donor molecule TBDTCNR and the fullerene acceptor molecule PC61BM for use in solution-processed small-molecule-based organic solar cells (SMOSCs). We found that the pseudo-two-dimensional fractal-like networks in the bulk heterojunction (BHJ) structure were determined by mutual interactions between the small-molecule (SM) crystallites and the nanoscale PC61BM clusters during their formation and phase separation, and deduced quantitatively, at multiple length scales, the BHJ structures comprising these SM crystallites and PC61BM clusters. We also conducted in situ GIWAXS measurements to study the temporal behavior and kinetics of SM crystallization from solution to the solid film state. Our GISAXS/GIWAXS study revealed that the multilength-scale BHJ structures in the thin films could be tuned effectively by varying the amount of incorporated PC61BM and the annealing temperature. This study provides fundamental information relating to the mechanism of formation of hierarchical BHJ structures through relatively rapid crystallization of a highly crystalline SM, as well as the relationships among the hierarchical structure, the photovoltaic performance, and the mechanism of formation, thereby allowing greater control over BHJ structures in SMOSCs with optimized fabrication and performance.
Superhelices with tunable twisting power directed from supramolecular pairing of focal asymmetry in achiral dendron-jacketed block copolymers
(2020-02-14)
Lin, I-Ming
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Chou, Che-Min
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Li, Ming-Chia
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Guo, Rong-Hao
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Lee, Cheng-Kuang
The formation of helical assemblies from achiral supramacromolecules has been a highly mysterious process, but is of interest for the generation of a variety of structures and properties. Herein, novel hierarchical superhelices are developed from self-assembly of achiral dendron-jacketed block copolymers (DJBCPs). The presence of focal asymmetry in both the stereochemistry of the dendrons (donors) and interactive binding sites of the copolymer chains (acceptors) plays a pivotal role in generating a spontaneous symmetry breaking through tailored donor-acceptor matching via hydrogen bonding. The focal asymmetry, on a scale of several nanometers, propagates to helical twists of the achiral DJBCP hierarchical assemblies over hundreds of nanometers, such that the primary molecular asymmetry sequentially triggers a secondary helical conformation of the dendron-jacketed blocks, then tertiary supramolecular helical assemblies and eventually quaternary superhelices. The helical twisting power of the superhelices is tunable using the dendron grafting ratio, indicating that the magnitude of helical twisting can be quantitatively adjusted from local to entire structures.
Surface and interface porosity of polymer/fullerene-derivative thin films revealed by contrast variation of neutron and X-ray reflectivity
(2011)
Liu, Heng-Jui
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Jeng, U-Ser
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Yamada, Norifumi L.
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Su, An-Chung
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Wu, Wei-Ru
Contrast variation of neutron and X-ray reflections has been adapted to reveal the film in-depth (vertical) composition profiles of the blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) for bulk heterojunction thin-film solar cells, with a PCBM/P3HT weight ratio of c = 0.6, 0.8 and 1.0. The X-ray scattering-length-density (SLD) profiles, extracted from X-ray reflectivity for the blend films spun-cast on Si wafer, exhibit a stratified film morphology of ca. 85 nm film thickness; the corresponding neutron SLD profiles extracted for the same films further elucidate a PCBM-enriched interfacial layer adjacent to the Si substrate. In contrast to the often assumed two-phase model, a three-phase model with porosity included as the third phase has to be used in deducing the absolute volume fractions of PCBM and P3HT from the complementary neutron and X-ray SLD profiles. In general, the thus deduced in-depth composition profiles for the blend films comprise a substantial surface layer (10-15 nm) of ca. 40% porosity, a 50 nm main layer with relatively uniform PCBM-P3HT composition, and a PCBM-enriched interface layer (similar to 20 nm) with similar to 15% porosity. Formation of the surface porosity is related to interfacial instability occurred in a transient surface layer upon film drying. Annealing at 150 degrees C influences modestly the vertical phase separation of the film, but drastically activates local phase separation for formation and growth of PCBM and P3HT nanodomains, as revealed by grazing incidence small/wide angle X-ray scattering. The surface/interface porosity features (overlooked in nearly all the previous studies) and the composition-dependent vertical phase separation bear hints in advancing device performance via interfacial morphology optimization.
Surface Layering and Supersaturation for Top-Down Nanostructural Development during Spin Coating of Polymer/Fullerene Thin Films
(2017-07-19)
Wu, Wei-Ru
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Su, Chun-Jen
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Chuang, Wei-Tsung
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Huang, Yen-Chih
;
Yang, Po-Wei
This study provides new evidence on a long postulated mechanism of phase separation in a polymer/fullerene mixture during spin coating for controlled nanodomains of oriented crystallization and heterojunctions that favor applications in polymer solar cells (PSCs). The simultaneous nanoscale phase separation and crystallization during spin coating of the mixture are traced using in situ grazing-incidence small-and wide-angle X-ray scattering. Combined with the complimentary results from time-resolved optical reflectance spectroscopy, transient stratification of the liquid film during the transition from the flow-to evaporation-dominated stage of spin coating is disclosed; the vertical liquid-liquid phase separation incubates a supersaturated skin layer where fullerene aggregation and polymer crystallization occur and develop concomitantly. Shortly after the transition, the near-surface structural development is largely pinned, leaving the solvent-rich bottom layer to diminish via solvent diffusion and evaporation through the thickened skin layer that finally condenses into the spin-coated film upon solvent depletion. The shear-enhanced surface layering and supersaturation for the surface-down nanostructural development are unexpected in all the existing structural models for PSCs. The mechanistic understanding of coupled vertical phase separation and local nanosegregation provides new insights and alternative strategy to the morphology control of spin-cast PSC active layers in particular and various solution-processed polymeric films in general.
Synthesis and side-chain isomeric effect of 4,9-/5,10-dialkylated-beta-angular-shaped naphthodithiophenes-based donor-acceptor copolymers for polymer solar cells and field-effect transistors
(2017-04-21)
Chiou, De-Yang
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Cao, Fong-Yi
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Hsu, Jhih-Yang
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Tsai, Che-En
;
Lai, Yu-Ying
A systematic methodology is developed to construct the angular-shaped beta-form naphthodithiophene (beta-aNDT) core with regiospecific substitution of two alkyl groups at its 4,9-or 5,10-positions via the base-induced double 6 pi-cyclization of dithienyldieneyne precursors, leading to the two isomeric 4,9-beta-aNDT and 5,10-beta-aNDT monomers. It is found that a more curved geometry of the beta-aNDT units intrinsically increases the solubility and thus the solution-processability of the resultant polymers. Therefore, beta-aNDT units are ideal for polymerization with an acceptor-containing monomer without the need for any solubilizing aliphatic side chains, which are considered the insulating portion that jeopardizes charge transport. Based on this consideration, the 4,9- and 5,10-dialkylated beta-aNDT monomers are polymerized with the non-alkylated DTFBT acceptor to afford two P4,9-beta NDTDTFBT and P5,10-beta NDTDTFBT copolymers for head-to-head comparison of the 4,9-inner/5,10-outer isomeric alkylation effect. It is found that 4,9-beta aNDT adopts a twisted conjugated structure due to the intramolecular steric repulsion between the inner branched side chains and the beta-hydrogens on the thiophene rings. The slightly twisted 4,9-beta-aNDT moiety allows P4,9-beta NDTDTFBT to have higher solubility upon polymerization and thus a higher molecular weight, which eventually induces a higher ordered packing structure in the thin film compared to P5,10-beta NDTDTFBT. As a result, P4,9-beta NDTDTFBT exhibits a higher OFET mobility of 0.18 cm(2) V-1 s(-1), and the P4,9-beta NDTDTFBT: PC71BM-based solar cell device also achieves a higher PCE of 7.23%, which is even better than the corresponding P4,9-alpha NDTDTFBT-based device.
Synthesis, molecular and photovoltaic/transistor properties of heptacyclic ladder-type di(thienobenzo)fluorene-based copolymers
(2016)
Lee, Chia-Hao
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Lai, Yu-Ying
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Cao, Fong-Yi
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Hsu, Jhih-Yang
;
Lin, Zong-Liang
We present a facile synthesis method to make a new ladder-type heptacyclic dithienobenzofluorene (DTBF) framework, where the central 2,7-fluorene unit is covalently fastened with two external thiophenes via two C=C bridges. A dieneyne-containing precursor undergoes DBU-induced double benzannulation to regiospecifically introduce two solubilizing 2-octyldodecyl side chains at 5,10-positions of DTBF. The rigid and coplanar Br-DTBF monomer with sufficient solubility was copolymerized with 5,6-difluoro-4,7-bis(5-(trimethylstannyl) thiophen-2-yl) benzo[c][1,2,5] thiadiazole (Sn-DTFBT) and 5,10-bis(5-(trimethylstannyl)thiophen-2-yl)naphtho[1,2-c: 5,6-c\'] bis([1,2,5] thiadiazole) (Sn-DTNT) via Stille coupling to furnish two donor-acceptor copolymers, PDTBFFBT and PDTBFNT, respectively. Their thermal, optical, electrochemical, molecular stacking and photovoltaic properties are investigated. PDTBFNT has a higher molecular weight, smaller optical and electrochemical band gaps, and stronger solid-state packing than PDTBFFBT. DFT calculations were carried out to gain insight into the electronic and structural properties of DTBF and its derivatives. Bulk heterojunction solar devices with the ITO/ZnO/polymers: PC71BM/MoO3/Ag configuration were fabricated. By adding 5 vol% diphenyl ether (DPE) as an additive, PDTBFNT: PC71BM and PDTBFFBT: PC71BM devices achieved the power conversion efficiencies of 5.22% and 2.68%, respectively. The superior efficiency of PDTBFNT over PDTBFFBT is attributed to the better LUMO energy alignment between PDTBFNT and PC71BM and the face-on p-stacking of PDTBFNT in the active layer. Moreover, PDTBFNT exhibited a higher field-effect transistor hole mobility of 1.90 x 10(-2) cm(2) V-1 s(-1) than PDTBFFBT with a value of 3.96 x 10(-3) cm(2) V-1 s(-1).
Two-dimensional densely packed DNA nanostructure derived from DNA complexation with a low-generation poly(amidoamine) dendrimer
(2007-01-30)
Su, Chun-Jen
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Liu, Yi-Chun
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Chen, Hsin-Lung
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Li, Yen-Cheng
;
Lin, Hsien-Kuang
One of the keys for using deoxyribonucleic acid (DNA) as a nanomaterial relies on how the individual DNA chain can be aligned and how a multitude of DNA chains can be packed into ordered nanostructures. Here we present a simple method for constructing a 2-D densely packed DNA nanostructure using the electrostatic complex of DNA with a poly(amidoamine) (PAMAM) dendrimer of generation two. Ordered DNA arrays are formed by drop-casting an aqueous solution containing positively overcharged complexes onto mica followed by a prolonged incubation. During the incubation, the complexes tend to adsorb onto the negatively charged mica surface through electrostatic attraction. The rodlike complexes organize to form ordered arrays to increase the surface density of the adsorbed complexes and hence the attractive free energy of adsorption. The densely packed nanostructure obtained here is distinguished from the previously reported spheroid or toroid structure derived from DNA complexations with the higher-generation dendrimers.