[Show abstract][Hide abstract] ABSTRACT: Photophysical properties of functionalized anthradithiophene (ADT) and pentacene (Pn) derivatives, as well as energy and charge transfer properties of donor-acceptor (D/A) pairs of these derivatives, are presented. The molecules studied were imaged on the single-molecule level in a polymeric and in a functionalized benzothiophene (BTBTB) crystalline host using room-temperature wide-field epifluorescence microscopy. The BTBTB host imposed orientational constraints on the guest molecules, depending on their functionalization. Flexibility of functionalization of both guest (ADT, Pn) and host (BTBTB) molecules can be used for systematic studies of nanoscale morphology and photophysics of D/A organic semiconductor bulk heterojunctions using single-molecule fluorescence microscopy.
Chemical Physics Letters 04/2015; 629. DOI:10.1016/j.cplett.2015.04.014 · 1.90 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The small-molecule organic semiconductor tetraceno[2,3-b]thiophene has been synthesized through an environmentally friendly synthetic route, utilizing NaBH4, rather than Al/HgCl2, for the reduction of the quinone. Low-voltage organic thin-film transistors (TFTs) have been fabricated using tetraceno[2,3-b]thiophene and, for comparison, pentacene and anthradithiophene as the semiconductor. The tetraceno[2,3-b]thiophene TFTs have an effective field-effect mobility as large as 0.55 cm2 V–1 s–1 and a subthreshold swing of 0.13 V/decade. In addition, it has been found that the contact resistance of the tetraceno[2,3-b]thiophene TFTs is substantially smaller than that of the anthradithiophene TFTs and similar to that of the pentacene TFTs. The long-term air stability of TFTs based on all three semiconductors has been monitored over a period of 12 months. The initial charge-carrier mobility of the tetraceno[2,3-b]thiophene TFTs is ∼50% smaller than that of the pentacene TFTs, but as a result of the greater ionization potential and better air stability induced by the terminal thiophene ring condensed at the thiophene-b-bond, the tetraceno[2,3-b]thiophene TFTs outperform the pentacene TFTs after continuous exposure to ambient air for just 3 months.
Chemistry of Materials 02/2015; 27(3):998-1004. DOI:10.1021/cm5043183 · 8.35 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The transition from an electrode-dominated ordered monolayer structure to a bulk-like thin film crystal structure of 2,8-difluoro-5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TES-ADT) is observed to occur over at least the first four molecular layers near the electrode surface. Scanning tunneling microscopy studies of the growth of diF-TES-ADT on Au(111) show that the first two molecular layers assemble with aromatic planes parallel to the substrate surface. The monolayer structures are highly stable and well-ordered, while the bilayer structures are more loosely packed and poorly ordered. Subsequent diF-TES-ADT growth results in a more bulk-like layer containing standing up molecular configurations approaching the (001) crystal face as observed by grazing incidence wide angle X-ray scattering measurements. However, the third and fourth monolayers also show poor long-range ordering and an apparent height modulation that indicate significant strain effects from the substrate still persist.
[Show abstract][Hide abstract] ABSTRACT: Triethylsilylethynyl anthradithiophene (TESADT) holds considerable promise for organic transistor applications due to the high electrical mobilities attained by post-deposition crystallization using solvent vapour annealing. We have studied thermal annealing as an alternative route to post-deposition crystallization of TESADT films. Thermal annealing initially appears promising, producing mm-sized crystal domains, but poor electrical performance is obtained, which we attribute to a combination of crack formation and potentially also structural transition during the anneal process. We also find that illumination has a significant positive effect on crystallization, possibly due to an optically-induced enhancement in molecular mobility during annealing. This suggests further studies of how solvent exposure, heat, substrate surface properties and particularly light exposure influence the ordering kinetics of TESADT are warranted.
[Show abstract][Hide abstract] ABSTRACT: We report hybrid organic/inorganic complementary circuits using ink-jet-printed fluorinated 5,11-bis(triethylsilylethynyl) anthradithiophene (diF-TESADT) as the p-channel material and zinc oxide deposited by plasma enhanced atomic layer deposition (PEALD) as the n-channel material. Using a mixed solvent system, discrete ink-jet printed diF-TESADT OTFTs have field effect mobility as large as 0.4 cm(2)/V s. PEALD ZnO TFTs typically have field-effect mobility >15 cm(2)/V s. Using p-type diF-TESADT and n-type ZnO active layers in a simple, 4-mask, 1 ink jet printing step, low temperature (<= 200 degrees C process we fabricated complimentary MOS (CMOS) inverters with maximum voltage gain of 35 and sub-pA leakage currents for both low and high input levels.
[Show abstract][Hide abstract] ABSTRACT: Trialkylgermyl functionalization allows development of high-performance soluble small-molecule organic semiconductors with mobilities greater than 5 cm(2) V(-1) s(-1) . Spray-deposited organic thin-film transistors show a record mobility of 2.2 cm(2) V(-1) s(-1) and demonstrate the potential for incorporation in large-area, low-cost electronic applications.
[Show abstract][Hide abstract] ABSTRACT: Despite the great interest organic spintronics has recently attracted, there is only a partial understanding of the fundamental physics behind electron spin relaxation in organic semiconductors. Mechanisms based on hyperfine interaction have been demonstrated, but the role of the spin-orbit interaction remains elusive. Here, we report muon spin spectroscopy and time-resolved photoluminescence measurements on two series of molecular semiconductors in which the strength of the spin-orbit interaction has been systematically modified with a targeted chemical substitution of different atoms at a particular molecular site. We find that the spin-orbit interaction is a significant source of electron spin relaxation in these materials.
[Show abstract][Hide abstract] ABSTRACT: The rich phase behavior of 5,11-bis(triethylsilylethynyl) anthradithiophene (TES ADT) – one of the most promising, solution-processable small-molecular organic semiconductors – is analyzed, revealing the highest performing polymorph among four solid-state phases, opening pathways toward the reliable fabrication of high-performance bottom-gate/bottom-contact transistors.
Chemistry of Materials 04/2013; 25(9):1823–1828. DOI:10.1021/cm400369w · 8.35 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Organic thin film transistors (OTFT) partially composed of solution
(diF-TES-ADT) have shown high performance with hole mobilities up to 1
cm^2/(V s). Pretreatment of the gold electrodes results in growth of
large diF-TES-ADT crystals extending well out into the channel of the
OTFT. Without electrode pretreatment, the crystal sizes are small and
possess a non-preferred molecular orientation. We have chosen to
investigate the reasons for the reduced crystal size of these films on
untreated gold electrodes by studying a model system generated by vapor
deposition of multilayers of diF-TES-ADT on Au(111). The initial wetting
layer forms a highly ordered film such that the anthradithiophene
backbone is oriented parallel to the substrate and the unit cell is 1.49
nm x 1.25 nm with an included angle of 56.8^o. The second
layer is poorly ordered with only weak evidence of crystallinity in
small regions. Growth beyond the second layer appears essentially
bulk-like and crystalline with domain sizes that are potentially limited
by the disordered bilayer growth.
[Show abstract][Hide abstract] ABSTRACT: We utilize scanning tunneling microscopy (STM) to characterize the
initial growth and crystallization of the high-performance, small
organic molecule 2,8-difluoro-5,11-triethylsilylethynyl (diF TESADT) on
Au(111). Two ordered structures are observed with diF TESADT backbone
planes parallel to the substrate. Submolecular resolution imaging of the
first monolayer ordered film regions realizes structures with close
approach of fluorine-sulfur and fluorine-fluorine atoms of alternating
molecules. These measurements provide evidence for the importance of
non-covalent F-S and F-F interactions in driving 2D self-assembly.
Scanning Tunneling Spectroscopy indicates a 2.4 eV transport gap which
is insensitive to the local domain. Structures and growth are put in
context of bulk measurements and device performance measurements.
[Show abstract][Hide abstract] ABSTRACT: We utilize Atomic Force Microscopy (AFM) and Kelvin Probe Force
Microscopy (KPFM) to characterize the dynamics of electronic transport
across 2,8-difluoro-5,11-triethylsilylethynyl anthradithiophene (diF
TESADT) grain boundaries. We show that the morphology of grain
boundaries and the adsorption of atmospheric dopants at these local
boundaries have a direct impact on the electrical behavior of diF TESADT
in thin film transistor (TFT) devices. Device voltage drops at grain
boundaries are characterized as a function of both atmospheric dopants
and transition time between dopants. The morphology, including
crystallization and packing motifs, of diF TESADT grown on thermally
grown SiO2 will be discussed and related to other
semiconducting small organic molecules. This work will be put in the
context of other, recent advances in small molecule organics.
[Show abstract][Hide abstract] ABSTRACT: The nanoscale boundaries formed when neighboring spherulites impinge in polycrystalline, solution-processed organic semiconductor thin films act as bottlenecks to charge transport, significantly reducing organic thin-film transistor mobility in devices comprising spherulitic thin films as the active layers. These interspherulite boundaries (ISBs) are structurally complex, with varying angles of molecular orientation mismatch along their lengths. We have successfully engineered exclusively low- and exclusively high-angle ISBs to elucidate how the angle of molecular orientation mismatch at ISBs affects their resistivities in triethylsilylethynyl anthradithiophene thin films. Conductive AFM and four-probe measurements reveal that current flow is unaffected by the presence of low-angle ISBs, whereas current flow is significantly disrupted across high-angle ISBs. In the latter case, we estimate the resistivity to be 22 MΩμm(2)/width of the ISB, only less than a quarter of the resistivity measured across low-angle grain boundaries in thermally evaporated sexithiophene thin films. This discrepancy in resistivities across ISBs in solution-processed organic semiconductor thin films and grain boundaries in thermally evaporated organic semiconductor thin films likely arises from inherent differences in the nature of film formation in the respective systems.
[Show abstract][Hide abstract] ABSTRACT: Scanning tunneling microscopy studies of the first monolayer of 2,8-difluoro-5,11-(bis)triethylsilylethynyl anthradithiophene on Au(111) reveal two ordered structures with anthradithiophene planes parallel to the substrate. Submolecular resolution STM images demonstrate structures with a close approach of fluorine–sulfur and fluorine–fluorine atoms in the ordered structures. This provides evidence for the importance of noncovalent F–S and F–F in driving 2D self-assembly in the monolayer. Spectroscopic studies indicate a transport gap of 2.4 eV that is insensitive to the local domain structures, as expected for weak intermolecular interactions.
The Journal of Physical Chemistry C 09/2012; 116(40):21465–21471. DOI:10.1021/jp307539q · 4.77 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Patterning organic thin-film transistors (OTFTs) is critical in achieving high electronic performance and low power consumption. We report on a high-yield, low-complexity patterning method based on exploiting the strong tendency of halogen-substituted organic semiconductors to crystallize along chemically tailored interfaces. We demonstrate that the organic semiconductor molecules self-align on the contacts, when the halogen–halogen interaction is allowed by the chemical structures and conformations of the self-assembled monolayer and organic semiconductor. The ordered films exhibit high mobilities and constrain the current paths. The regions surrounding the devices, where the interaction is inhibited, consist of randomly oriented molecules, exhibiting high-resistivity and electrically insulating neighboring devices. To identify the role of F–F interactions in the development of crystalline order, we investigate OTFTs fabricated on mono-fluorinated benzene thiol treated contacts, which allows us to isolate the interactions between the F originating from the organic semiconductor and the F in each position on the benzene ring of the thiol, and to selectively study the role of each interaction. Combining the results obtained from quantitative grazing incidence X-ray diffraction and Kelvin probe measurements, we show that the surface treatments induce structural changes in the films, but also alter the injection picture as a result of work function shifts that they introduce. We show that both effects yield variations in the field-effect transistor characteristics, and we are able to tune the field-effect mobility more than two orders of magnitude in the same material.
[Show abstract][Hide abstract] ABSTRACT: Heterogeneous nucleation is often the precursor to crystallization in solution-processed organic semiconductor thin films. Here, we study the efficacy of a series of nine small-molecule organic semiconductor additives in seeding the crystallization of solution-processable triethylsilylethynyl anthradithiophene (TES ADT). By systematically varying the concentrations of the additives in TES ADT thin films, we found the tendency of the additives to crystallize, their solubility in the casting solvent, and their similarity in chemical structure to TES ADT, to determine the nucleation and resulting density of nuclei. Tracking the crystallization process further yields information about the mechanism of nucleation. While pure TES ADT nucleates instantaneously at the onset of crystallization, nucleation transitions to a distributed process occurring throughout crystallization with the incorporation of increasing amounts of additives.
Chemistry of Materials 07/2012; 24(15):2920–2928. DOI:10.1021/cm3010858 · 8.35 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Herein, time-dependent scanning Kelvin probe microscopy of solution processed organic thin film transistors (OTFTs) reveals a correlation between film microstructure and OTFT device performance with the location of trapped charge within the device channel. The accumulation of the observed trapped charge is concurrent with the decrease in ISD during operation (VG = −40 V, VSD = −10 V). We discuss the charge trapping and dissipation dynamics as they relate to the film structure and show that application of light quickly dissipates the observed trapped charge.
[Show abstract][Hide abstract] ABSTRACT: The growth rate of spherulites in solution-processed, triethylsilylethynyl anthra-dithiophene thin films can vary by a factor of three depending on the surface energy of the underlying substrate. By selectively patterning the underlying substrate to have regions of different surface energies, Y.-L. Loo and co-workers show on page 2692 how they are able to guide crystallization along pre-specified, nonlinear patterns over large areas in the plane of the film.
[Show abstract][Hide abstract] ABSTRACT: Control over the molecular orientation in organic thin films is demonstrated with precise in-plane spatial resolution over large areas. By exploiting the differential crystallization rates on substrates with different surface energies, the radial symmetry of spherulitic growth can be disrupted by preferentially selecting the molecular orientations that promote growth along the paths of the underlying patterns.
[Show abstract][Hide abstract] ABSTRACT: The preparation of uniform large-area highly crystalline organic semiconductor thin films that show outstanding carrier mobilities remains a challenge in the field of organic electronics, including organic field-effect transistors. Quantitative control over the drying speed during dip-coating permits optimization of the organic semiconductor film formation, although the kinetics of crystallization at the air–solution–substrate contact line are still not well understood. Here, we report the facile one-step growth of self-aligning,
highly crystalline soluble acene crystal arrays that exhibit excellent field-effect mobilities (up to 1.5 cm V^−1s^−1) via an optimized dip-coating process. We discover that optimized acene crystals grew at a particular substrate lifting-rate in the presence of low boiling point solvents, such as dichloromethane (b.p. of 40.0 °C) or chloroform (b.p. of 60.4 °C). Variable-temperature dip-coating experiments using various solvents and lift rates are performed to elucidate the crystallization behavior. This bottom-up study of soluble acene crystal growth during dip-coating provides conditions under which one may obtain uniform organic semiconductor crystal arrays with high crystallinity and mobilities over large substrate areas, regardless of the substrate geometry (wafer substrates or cylinder-shaped substrates).
[Show abstract][Hide abstract] ABSTRACT: Due to the rapidity of morphological development during deposition, solution-processed organic semiconductor thin films exist in semicrystalline or polycrystalline states, incorporating a high degree of local variations in molecular orientation compared to their single-crystal counterparts. Spherulites, a common crystalline superstructure found in these systems, for example, incorporate a large distribution of molecular orientations about the radial axis to maintain their space-filling growth habit. Here, we aim to determine how this distribution of molecular orientations influences charge transport by fabricating arrays of devices on single spherulites. Given that the orientation distribution that is present about the radial axis mandates the presence of low-angle grain boundaries within single spherulites, we find intraspherulitic charge transport to be independent of the general direction of π-stacking; organic field-effect transistors exhibit comparable mobilities regardless of how their channels are oriented with respect to the general π-stacking direction.
Journal of the American Chemical Society 02/2012; 134(12):5436-9. DOI:10.1021/ja2116316 · 12.11 Impact Factor