Ferdinand S. Melkonyan

Bithiophenesulfonamide Building Block for π-Conjugated Donor–Acceptor Semiconductors

We report here π-conjugated small molecules and polymers based on the new π-acceptor building block, bithiophenesulfonamide (BTSA). Molecular orbital computations and optical, electrochemical, and crystal structure analyses illuminate the architecture and electronic structure of the BTSA unit versus other acceptor building blocks. Field-effect transistors and photovoltaic cells demonstrate that BTSA is a promising unit for the construction of π-conjugated semiconducting materials.

UV-Ozone Interfacial Modification in Organic Transistors for High-Sensitivity NO2 Detection

A new type of nitrogen dioxide (NO2 ) gas sensor based on copper phthalocyanine (CuPc) thin film transistors (TFTs) with a simple, low-cost UV-ozone (UVO)-treated polymeric gate dielectric is reported here. The NO2 sensitivity of these TFTs with the dielectric surface UVO treatment is ≈400× greater for [NO2 ] = 30 ppm than for those without UVO treatment. Importantly, the sensitivity is ≈50× greater for [NO2 ] = 1 ppm with the UVO-treated TFTs, and a limit of detection of ≈400 ppb is achieved with this sensing platform. The morphology, microstructure, and chemical composition of the gate dielectric and CuPc films are analyzed by atomic force microscopy, grazing incident X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, revealing that the enhanced sensing performance originates from UVO-derived hydroxylated species on the dielectric surface and not from chemical reactions between NO2 and the dielectric/semiconductor components. This work demonstrates that dielectric/semiconductor interface engineering is essential for readily manufacturable high-performance TFT-based gas sensors.

Hole-Transfer Dependence on Blend Morphology and Energy Level Alignment in Polymer: ITIC Photovoltaic Materials

Bulk-heterojunction organic photovoltaic materials containing nonfullerene acceptors (NFAs) have seen remarkable advances in the past year, finally surpassing fullerenes in performance. Indeed, acceptors based on indacenodithiophene (IDT) have become synonymous with high power conversion efficiencies (PCEs). Nevertheless, NFAs have yet to achieve fill factors (FFs) comparable to those of the highest-performing fullerene-based materials. To address this seeming anomaly, this study examines a high efficiency IDT-based acceptor, ITIC, paired with three donor polymers known to achieve high FFs with fullerenes, PTPD3T, PBTI3T, and PBTSA3T. Excellent PCEs up to 8.43% are achieved from PTPD3T:ITIC blends, reflecting good charge transport, optimal morphology, and efficient ITIC to PTPD3T hole-transfer, as observed by femtosecond transient absorption spectroscopy. Hole-transfer is observed from ITIC to PBTI3T and PBTSA3T, but less efficiently, reflecting measurably inferior morphology and nonoptimal energy level alignment, resulting in PCEs of 5.34% and 4.65%, respectively. This work demonstrates the importance of proper morphology and kinetics of ITIC → donor polymer hole-transfer in boosting the performance of polymer:ITIC photovoltaic bulk heterojunction blends.

Carbohydrate-Assisted Combustion Synthesis to Realize High-Performance Oxide Transistors

Owing to high carrier mobilities, good environmental/thermal stability, excellent optical transparency, and compatibility with solution processing, thin-film transistors (TFTs) based on amorphous metal oxide semiconductors (AOSs) are promising alternatives to those based on amorphous silicon (a-Si:H) and low-temperature (<600 °C) poly-silicon (LTPS). However, solution-processed display-relevant indium-gallium-tin-oxide (IGZO) TFTs suffer from low carrier mobilities and/or inferior bias-stress stability versus their sputtered counterparts. Here we report that three types of environmentally benign carbohydrates (sorbitol, sucrose, and glucose) serve as especially efficient fuels for IGZO film combustion synthesis to yield high-performance TFTs. The results indicate that these carbohydrates assist the combustion process by lowering the ignition threshold temperature and, for optimal stoichiometries, enhancing the reaction enthalpy. IGZO TFT mobilities are increased to >8 cm(2) V(-1) s(-1) on SiO2/Si gate dielectrics with significantly improved bias-stress stability. The first correlations between precursor combustion enthalpy and a-MO densification/charge transport are established.

Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport

Significance Shear-printing of electroactive polymers using natural brushes is a promising film deposition technique for printed electronics capable of microstructure control and electrical properties enhancement over large areas. Nevertheless, the interplay between film printing parameters, microstructure development, and charge transport is not well-understood. We report that natural brush-printing greatly enhances charge transport by as much as 5.7× through control of polymer nanofibril aggregate growth and backbone alignment, attributable to the oriented squamae of the natural hair. However, while brush shear-induced aggregation enhances charge transport, we show that backbone alignment alone does not guarantee charge transport anisotropy. These results provide additional understanding of shear-induced enhanced charge transport and set processing guidelines for high-performance printed organic circuitry. Shear-printing is a promising processing technique in organic electronics for microstructure/charge transport modification and large-area film fabrication. Nevertheless, the mechanism by which shear-printing can enhance charge transport is not well-understood. In this study, a printing method using natural brushes is adopted as an informative tool to realize direct aggregation control of conjugated polymers and to investigate the interplay between printing parameters, macromolecule backbone alignment and aggregation, and charge transport anisotropy in a conjugated polymer series differing in architecture and electronic structure. This series includes (i) semicrystalline hole-transporting P3HT, (ii) semicrystalline electron-transporting N2200, (iii) low-crystallinity hole-transporting PBDTT-FTTE, and (iv) low-crystallinity conducting PEDOT:PSS. The (semi-)conducting films are characterized by a battery of morphology and microstructure analysis techniques and by charge transport measurements. We report that remarkably enhanced mobilities/conductivities, as high as 5.7×/3.9×, are achieved by controlled growth of nanofibril aggregates and by backbone alignment, with the adjusted R2 (R2adj) correlation between aggregation and charge transport as high as 95%. However, while shear-induced aggregation is important for enhancing charge transport, backbone alignment alone does not guarantee charge transport anisotropy. The correlations between efficient charge transport and aggregation are clearly shown, while mobility and degree of orientation are not always well-correlated. These observations provide insights into macroscopic charge transport mechanisms in conjugated polymers and suggest guidelines for optimization.

Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers

We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μe and μh of up to 0.39 and 0.32 cm2/(V·s), respectively.

Closely packed, low reorganization energy π-extended postfullerene acceptors for efficient polymer solar cells

Significance For producing electricity, polymer solar cells (PSCs) offer properties tunability, light weight, scalability, and earth-abundant materials. PSC active layers typically consist of donor polymer and fullerene acceptor blends having discrete conduits for photogenerated hole and electron conduction. The spherical fullerene shape, which enables close packing, orbital degeneracies, and low charge-transfer reorganization energies, is thought to be essential for efficient photocurrent generation and high power conversion efficiencies (PCEs). However, the recent advent of irregularly shaped indacenodithienothiophene (IDTT) acceptors yielding higher PCEs challenges the fullerene paradigm. In a combined experimental and theoretical study with two new isomeric IDTT derivatives, we shed light on the basis of this performance in terms of surprisingly close molecular packing, strong electronic coupling, and low reorganization energies. New organic semiconductors are essential for developing inexpensive, high-efficiency, solution-processable polymer solar cells (PSCs). PSC photoactive layers are typically fabricated by film-casting a donor polymer and a fullerene acceptor blend, with ensuing solvent evaporation and phase separation creating discrete conduits for photogenerated holes and electrons. Until recently, n-type fullerene acceptors dominated the PSC literature; however, indacenodithienothiophene (IDTT)-based acceptors have recently enabled remarkable PSC performance metrics, for reasons that are not entirely obvious. We report two isomeric IDTT-based acceptors 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz-(5, 6)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]di-thiophene (ITN-C9) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz(6,7)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2′,3′-d′]-s-indaceno[1,2-b:5,6-b′]dithiophene (ITzN-C9) that shed light on the exceptional IDTT properties vis-à-vis fullerenes. The neat acceptors and blends with fluoropolymer donor poly{[4,8-bis[5-(2- ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene2,6-diyl]-alt-[2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo4H,8H-benzo[1,2-c:4,5-c′]dithiophene-1,3-diyl]]} (PBDB-TF) are investigated by optical spectroscopy, cyclic voltammetry, thermogravimetric analysis, differential scanning calorimetry, single-crystal X-ray diffraction, photovoltaic response, space-charge-limited current transport, atomic force microscopy, grazing incidence wide-angle X-ray scattering, and density functional theory-level quantum chemical analysis. The data reveal that ITN-C9 and ITzN-C9 organize such that the lowest unoccupied molecular orbital-rich end groups have intermolecular π−π distances as close as 3.31(1) Å, with electronic coupling integrals as large as 38 meV, and internal reorganization energies as small as 0.133 eV, comparable to or superior to those in fullerenes. ITN-C9 and ITzN-C9 have broad solar-relevant optical absorption, and, when blended with PBDB-TF, afford devices with power conversion efficiencies near 10%. Performance differences between ITN-C9 and ITzN-C9 are understandable in terms of molecular and electronic structure distinctions via the influences on molecular packing and orientation with respect to the electrode.

Even and odd oligothiophene-bridged bis-naphthalimides for n-type and ambipolar organic field effect transistors

The synthesis and characterization of a new family of thiophene bridged bis-naphthalimides (2NDI-XT) are presented here. These semiconductors have been designed to have an even or an odd number of thiophene rings, with the aim of studying molecules with varying and alternant molecular dipolar moments, which are expected to significantly impact molecular packing. Following a theoretical analysis, the stability of a series of π-dimers showing either parallel or antiparallel packing dispositions has been predicted. Our results point out to a molecular packing motif in which both the NDI and oligothiophene fragments are cofacial for all the semiconductors investigated, regardless of their estimated molecular dipole moments. These, in principle, unexpected results are in good agreement with the field-effect mobilities measured in a bottom-gate top-contact transistor architecture, which show no straightforward correlation between device performance and dipolar moment. Ambipolar field-effect mobilities are recorded for the most extended π-systems, 5,5′-bis(2-hexyldecylbenzo[lmn]thieno[3′,4′:4,5]imidazo[2,1-b][3,8]phenanthroline-1,3,6(2H)-trione-10-yl)-2,2′-bithiophene, 2NDI-4T and 5,5′′-bis(2-hexyldecylbenzo[lmn]thieno[3′,4′:4,5]imidazo[2,1-b][3,8]phenanthroline-1,3,6(2H)-trione-10-yl)-2,2′:5′,2′′-terthiophene, 2NDI-5T, with the latter showing quite balanced electron and hole mobilities of 1.8 × 10−3 cm2 V−1 s−1 and 8.4 × 10−3 cm2 V−1 s−1, respectively.