Elucidating the time-dependent charge neutrality point modulation of polymer-coated graphene field-effect transistors in an ambient environment.

The charge neutrality point (CNP) is one of the essential parameters in the development of graphene field-effect transistors (GFETs). For GFET with an intrinsic graphene channel layer, the CNP is typically near-zero-volt gate voltage, implying that a well-balanced density of electrons and holes exists in the graphene channel layer. Fabricated GFET, however, typically exhibits CNP that is either positively or negatively shifted from the near-zero-volt gate voltage, implying that the graphene channel layer is unintentionally doped, leading to a unipolar GFET transfer characteristic. Furthermore, the CNP is also modulated in time, indicating that charges are dynamically induced in the graphene channel layer. In this work, understanding and mitigating the CNP shift were attempted by introducing passivation layers made of polyvinyl alcohol and polydimethylsiloxane onto the graphene channel layer. The CNP was found to be negatively shifted, recovered back to near-zero-volt gate voltage, and then positively shifted in time. By analyzing the charge density, carrier mobility, and correlation between the CNP and the charge density, it can be concluded that positive CNP shifts can be attributed to the charge trapping at the graphene/SiO2interface. The negative CNP shift, on the other hand, is caused by dipole coupling between dipoles in the polymer layer and carriers on the surface of the graphene layer. By gaining a deeper understanding of the intricate mechanisms governing the CNP shifts, an ambiently stable GFET suitable for next-generation electronics could be realized.

Self-Assembly Behavior, Aggregation Structure, and the Charge Carrier Transport Properties of S-Heterocyclic Annulated Perylene Diimide Derivatives.

The construction of high-performance n-type semiconductors is crucial for the advancement of organic electronics. As an attractive n-type semiconductor, molecular systems based on perylene diimide derivatives (PDIs) have been extensively investigated over recent years. Owing to the fascinating aggregated structure and high performance, S-heterocyclic annulated PDIs (SPDIs) are receiving increasing attention. However, the relationship between the structure and the electrical properties of SPDIs has not been deeply revealed, restricting the progress of PDI-based organic electronics. Here, we developed two novel SPDIs with linear and dendronized substituents in the imide position, named linear SPDI and dendronized SPDI, respectively. A series of structural and property characterizations indicated that linear SPDI formed a long-range-ordered crystalline structure based on helical supramolecular columns, while dendronized SPDI, with longer alkyl side chains, formed a 3D-ordered crystalline structure at a low temperature, which transformed into a hexagonal columnar liquid crystal structure at a high temperature. Moreover, no significant charge carrier transport signal was examined for linear SPDI, while dendronized SPDI had a charge carrier mobility of 3.5 × 10-3 cm2 V-1 s-1 and 2.1 × 10-3 cm2 V-1 s-1 in the crystalline and liquid crystalline state, respectively. These findings highlight the importance of the structure-function relationship in PDIs, and also offer useful roadmaps for the design of high-performance organic electronics for down-to-earth applications.

Highly Soluble Ambipolar anti-Perylene-3,4 : 9,10-bis(benzimidazole)s Stabilize a Room-Temperature Columnar Hexagonal Phase.

A new series of highly soluble perylene anti-bis(4,5-dialkoxybenzimidazole)s bearing branched flexible chains stabilizing room temperature columnar hexagonal phase and with balanced ambipolar charge carrier mobility is reported for the first time. Only the anti isomer was successfully separated and characterized. These compounds have a high extinction coefficient, small optical band gap and wide absorption range, thus making them a promising class of ambipolar organic semiconductors capable of self-organizing.

A study of 2D GeI2/InTe van der Waals hetero bilayer as a photocatalyst material.

The computational study of the van der Waals hetero (vdW) bilayer GeI2/InTe has been carried out in present study. The isolated monolayer GeI2and InTe have been studied first and the results were compared to the previous studies. The possible stackings are considered after the vdW interaction correction is applied in the structure relaxation. The vdW hetero bilayer stability has been checked from the phonon dispersion andab initioMolecular Dynamics calculations. The charge transfer from InTe to GeI2monolayer. Type-II indirect band gap (1.98, 2.01 eV) is verified by the projected band structure and band alignment calculations. The vdW hetero bilayer is a superior photocatalyst for the pH value up to pH = 0 to 11. The optical properties are calculated from the complex dielectric constant. The absorption coefficient shows the enhance absorption of light in the visible and ultraviolet regions. The vdW hetero bilayer has shown low reflectivity (37%) and a high refractive index (2.80) in the visible region. The enhanced optical properties have shown its possible applications in optoelectronic devices.

Photoconduction and Electroluminescence of Copper (II) Protoporphyrin and Chlorin Cu-C-e6.

Cu (II) protoporphyrin Cu-PP-IX and chlorin Cu-C-e6 were found to have both thin solid film formation and charge carrier transport abilities. In the layers deposited by resistive thermal evaporation, the mobilities of holes and electrons are on the order of 10-5 cm2 V-1 s-1. Organic light-emitting diodes incorporating the dye molecules as emitting dopants demonstrate electroluminescence in the UV and near-IR ranges.

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility.

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives (1 and 2) as subunits of 8-AGNR, with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR. The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm2  V-1 s-1 for the 8-AGNR.

High-Mobility Naphthalene Diimide Derivatives Revealed by Raman-Based In Silico Screening.

Charge transport in crystalline organic semiconductors (OSCs) is considerably hindered by low-frequency vibrations introducing dynamic disorder in the charge transfer integrals. Recently, we have shown that the contributions of various vibrational modes to the dynamic disorder correlate with their Raman intensities and suggested a Raman-based approach for estimation of the dynamic disorder and search for potentially high-mobility OSCs. In the present paper, we showcase this approach by revealing the highest-mobility OSC(s) in two series of crystalline naphthalene diimide derivatives bearing alkyl or cycloalkyl substituents. In contrast to our previous studies, Raman spectra are not measured, but are instead calculated using periodic DFT. As a result, an OSC with a potentially high charge mobility is revealed in each of the two series, and further mobility calculations corroborate this choice. Namely, for the naphthalene diimide derivatives with butyl and cyclopentyl substituents, the estimated room-temperature isotropic electron mobilities are as high as 6 and 15 cm2 V-1 s-1, respectively, in the latter case even exceeding 20 cm2 V-1 s-1 in a two-dimensional plane. Thus, our results highlight the potential of using the calculated Raman spectra to search for high-mobility crystalline OSCs and reveal two promising OSCs, which were previously overlooked.

Module-Patterned Polymerization towards Crystalline 2D sp2 -Carbon Covalent Organic Framework Semiconductors.

Despite rapid progress over the past decade, most polycondensation systems even upon a small structural variation of the building units eventually result in amorphous polymers other than the desired crystalline covalent organic frameworks. This synthetic dilemma is a central and challenging issue of the field. Here we report a novel approach based on module-patterned polymerization to enable efficient and designed synthesis of crystalline porous polymeric frameworks. This strategy features a wide applicability to allow the use of various knots of different structures, enables polycondensation with diverse linkers, and develops a diversity of novel crystalline 2D polymers and frameworks, as demonstrated by using the C=C bond-formation polycondensation reaction. The new sp2 -carbon frameworks are highly emissive and enable up-conversion luminescence, offer low band gap semiconductors with tunable band structures, and achieve ultrahigh charge mobilities close to theoretically predicted maxima.

Electrical Methods to Elucidate Charge Transport in Hybrid Perovskites Thin Films and Devices.

The panchromatic light absorption and excellent charge carrier transport properties in organo lead halide perovskites allowed to achieve an unprecedented power conversion efficiency in excess of 25 % for thin film photovoltaics fabrication. To understand the underlying phenomena, various comprehensive set of optical and electrical techniques have been employed to investigate the charge carrier dynamics in such devices. In this perspective, we aim to summarize the electrical transport properties of perovskite thin films by using (i) impedance spectroscopy (IS), (ii) space charge limited current (SCLC), (iii) field-effect transistors (FETs) and (iv) time-of-flight (TOF) methods. We have deliberated various equivalent circuit used to model the perovskite solar cells by means of IS. The SCLC technique provide vital electrical parameters such as mobility, activation energy, traps density and distribution, carrier concentration, density of states, etc. The TOF technique measures mobility as a primary parameter while the FETs configuration provide a valuable insight into the in-plane charge transport in perovskites thin films. We believe that these notable understanding will provide insights into charge carrier dynamics in perovskite materials and devices.

Crossover from band-like to thermally activated charge transport in organic transistors due to strain-induced traps.

The temperature dependence of the charge-carrier mobility provides essential insight into the charge transport mechanisms in organic semiconductors. Such knowledge imparts critical understanding of the electrical properties of these materials, leading to better design of high-performance materials for consumer applications. Here, we present experimental results that suggest that the inhomogeneous strain induced in organic semiconductor layers by the mismatch between the coefficients of thermal expansion (CTE) of the consecutive device layers of field-effect transistors generates trapping states that localize charge carriers. We observe a universal scaling between the activation energy of the transistors and the interfacial thermal expansion mismatch, in which band-like transport is observed for similar CTEs, and activated transport otherwise. Our results provide evidence that a high-quality semiconductor layer is necessary, but not sufficient, to obtain efficient charge-carrier transport in devices, and underline the importance of holistic device design to achieve the intrinsic performance limits of a given organic semiconductor. We go on to show that insertion of an ultrathin CTE buffer layer mitigates this problem and can help achieve band-like transport on a wide range of substrate platforms.

Principles of Structural Design of Conjugated Polymers Showing Excellent Charge Transport toward Thermoelectrics and Bioelectronics Applications.

Conjugated polymers, especially their second generation with a donor-acceptor alternating structure, have promising properties. These are suitable for two emerging fields, thermoelectrics and bioelectronics, if appropriate structural designs are implemented. This review aims to give a perspective for the potential and challenges of novel conjugated polymers in such applications. In particular, the aspects of synthetic design and the consequences of modifications of the chemical structure on the charge transport in selected second-generation conjugated polymers are reviewed. By understanding the effects of structural motifs on the overall material properties, polymers can be specifically tailored for the respective application. The basics of charge transport measurements are briefly summarized, as the charge transport plays an important role for thermoelectrics as well as for bioelectronics. In particular, the correlation between the reported charge carrier mobility values and the structural design of the polymers is reviewed. Examples of the application of second-generation conducting polymers in thermoelectrics and bioelectronics are shown to demonstrate the current state of research. Finally, the prospect of a purposeful design of new materials for these two emerging fields is discussed.

Metal Halide Perovskites: Synthesis, Ion Migration, and Application in Field-Effect Transistors.

The past several years have witnessed tremendous developments of metal halide perovskite (MHP)-based optoelectronics. Particularly, the intensive research of MHP-based light-emitting diodes, photodetectors, and solar cells could probably reform the optoelectronic semiconductor industry. In comparison, in spite of the large intrinsic charge carrier mobility of MHPs, the development of MHP-based field-effect transistors (MHP-FETs) is relatively slow, which is essentially due to the gate-field screening effect induced by the ion migration and accumulation in MHP-FETs. This work mainly aims to summarize the recent important work on MHP-FETs and propose solutions in terms of the development bottleneck of perovskite-based transistors, in an attempt to boost the research of MHP transistors further. First, the advantages and potential applications of MHP-FETs are briefly introduced, which is followed by a detailed description of the MHP crystalline structure and various material fabrication techniques. Afterward, MHP-FETs are discussed, including transistors based on hybrid organic-inorganic perovskites, all-inorganic perovskites, and lead-free perovskites.

Supramolecular Chirality Issues in Unorthodox Naphthalene Diimide Gelators.

Herein, the self-assembly of a few 1,3-dihydroxyl functionalized naphthalene diimide (NDI) derivatives has been reported with particular emphasis on the impact of chirality on gelation and the effect of self-assembly on charge-carrier mobility. A nonconventional gelator (R)-NDI, devoid of any long alkyl chains, exhibited spontaneous gelation in tetra-chloroethylene (TCE). Based on X-ray crystallography and powder X-ray diffraction studies, it was established that a ladder-like hydrogen-bonded chain formation between the 1,3-dihydroxyl group leads to the fibrillar structures with preferential helicity. Likewise the (S)-isomer also exhibited identical gelation and mesoscopic structure but produced fibrils with the opposite handedness. Intriguingly, an equimolar mixture of the (R)- and (S)-isomers did not show any gelation ability, rather a macroscopic precipitation was observed and, in sharp contrast to the individual isomers, the morphology of the mixture showed ill-defined near spherical agglomerates. Differential scanning calorimetry (DSC) studies revealed an identical crystallization peak for the supramolecular polymer produced from the enantiopure gelators ((R)- or (S)-isomer), which was absent in their equimolar mixture. However, mixtures of the two isomers with enantiomeric excess retrieved the gelation ability and preferential helicity demonstrating that chiral amplification is operative in the present system through the so-called "majority rule" effect. Chirality induction was also realized by the "sergeant and soldier" principle in the supramolecular assembly of an achiral NDI gelator in the presence of either the (R)- or (S)-isomer as the chiral dopant. However, the strong helical bias induced by the chiral gelator was found to be opposite in nature compared to that found in the self-assembly of the pure chiral gelator that has been rarely reported in the literature. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements indicated the strong positive impact of the gelation on the electrical conductivity.

Opto-electronic characterization of third-generation solar cells.

We present an overview of opto-electronic characterization techniques for solar cells including light-induced charge extraction by linearly increasing voltage, impedance spectroscopy, transient photovoltage, charge extraction and more. Guidelines for the interpretation of experimental results are derived based on charge drift-diffusion simulations of solar cells with common performance limitations. It is investigated how nonidealities like charge injection barriers, traps and low mobilities among others manifest themselves in each of the studied cell characterization techniques. Moreover, comprehensive parameter extraction for an organic bulk-heterojunction solar cell comprising PCDTBT:PC70BM is demonstrated. The simulations reproduce measured results of 9 different experimental techniques. Parameter correlation is minimized due to the combination of various techniques. Thereby a route to comprehensive and accurate parameter extraction is identified.

Rodlike Tetracene Derivatives.

Efficient and versatile synthetic access to rodlike tetracene derivatives was developed by means of Diels-Alder cycloaddition, halogenation, halogen-metal exchange, and transition metal mediated coupling reactions. Herein, the synthesis and structural, electrical, and charge-transport properties of three of the resulting materials, namely, 2-(tetracen-2-yl)tetracene, 1,4-bis(2-tetracenyl)benzene, and 2,5-bis(2-tetracenyl)thiophene, are presented. Good crystallization behavior on SiO2 substrates, narrowing of the bandgap by 0.2 eV, and a decrease of the ionization potential of more than 0.5 eV compared to tetracene were observed. Charge-carrier field-effect mobilities on the order of 10-1  cm2 V-1 s-1 , on/off ratios of 105 , and threshold voltages Vth <15 V were found in thin-film organic field-effect transistors prepared by standard high-vacuum deposition techniques.

A Solution-Processable Liquid-Crystalline Semiconductor for Low-Temperature-Annealed Air-Stable N-Channel Field-Effect Transistors.

A new solution-processable and air-stable liquid-crystalline n-channel organic semiconductor (2,2'-(2,8-bis(5-(2-octyldodecyl)thiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile, α,ω-2OD-TIFDMT) with donor-acceptor-donor (D-A-D) π conjugation has been designed, synthesized, and fully characterized. The new semiconductor exhibits a low LUMO energy (-4.19 eV) and a narrow optical bandgap (1.35 eV). The typical pseudo-focal-conic fan-shaped texture of a hexagonal columnar liquid-crystalline (LC) phase was observed over a wide temperature range. The spin-coated semiconductor thin films show the formation of large (≈0.5-1 µm) and highly crystalline platelike grains with edge-on molecular orientations. Low-temperature-annealed (50 °C) top-contact/bottom-gate OFETs have provided good electron mobility values as high as 0.11 cm2 (V s)-1 and high Ion /Ioff ratios of 107 to 108 with excellent ambient stability. This indicates an enhancement of two orders of magnitude (100×) when compared with the ß-substituted parent semiconductor, ß-DD-TIFDMT (2,2'-(2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile). The current rational alkyl-chain engineering route offers great advantages for D-A-D π-core coplanarity in addition to maintaining good solubility in organic solvents, and leads to favorable optoelectronic/physicochemical characteristics. These remarkable findings demonstrate that α,ω-2OD-TIFDMT is a promising semiconductor material for the development of n-channel OFETs on flexible plastic substrates and LC-state annealing of the columnar liquid crystals can lower the electron mobility for transistor-type charge transport.

Charge-Carrier Dynamics in 2D Hybrid Metal-Halide Perovskites.

Hybrid metal-halide perovskites are promising new materials for use in solar cells; however, their chemical stability in the presence of moisture remains a significant drawback. Quasi two-dimensional (2D) perovskites that incorporate hydrophobic organic interlayers offer improved resistance to degradation by moisture, currently still at the cost of overall cell efficiency. To elucidate the factors affecting the optoelectronic properties of these materials, we have investigated the charge transport properties and crystallographic orientation of mixed methylammonium (MA)-phenylethylammonium (PEA) lead iodide thin films as a function of the MA-to-PEA ratio and, thus, the thickness of the "encapsulated" MA lead-halide layers. We find that monomolecular charge-carrier recombination rates first decrease with increasing PEA fraction, most likely as a result of trap passivation, but then increase significantly as excitonic effects begin to dominate for thin confined layers. Bimolecular and Auger recombination rate constants are found to be sensitive to changes in electronic confinement, which alters the density of states for electronic transitions. We demonstrate that effective charge-carrier mobilities remain remarkably high (near 10 cm2V-1s-1) for intermediate PEA content and are enhanced for preferential orientation of the conducting lead iodide layers along the probing electric field. The trade-off between trap reduction, electronic confinement, and layer orientation leads to calculated charge-carrier diffusion lengths reaching a maximum of 2.5 µm for intermediate PEA content (50%).

Temperature and layer thickness dependent in situ investigations on epindolidione organic thin-film transistors.

We report on in situ performance evaluations as a function of layer thickness and substrate temperature for bottom-gate, bottom-gold contact epindolidione organic thin-film transistors on various gate dielectrics. Experiments were carried out under ultra-high vacuum conditions, enabling quasi-simultaneous electrical and surface analysis. Auger electron spectroscopy and thermal desorption spectroscopy (TDS) were applied to characterize the quality of the substrate surface and the thermal stability of the organic films. Ex situ atomic force microscopy (AFM) was used to gain additional information on the layer formation and surface morphology of the hydrogen-bonded organic pigment. The examined gate dielectrics included SiO2, in its untreated and sputtered forms, as well as the spin-coated organic capping layers poly(vinyl-cinnamate) (PVCi) and poly((±)endo,exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, diphenylester) (PNDPE, from the class of polynorbornenes). TDS and AFM revealed Volmer-Weber island growth dominated film formation with no evidence of a subjacent wetting layer. This growth mode is responsible for the comparably high coverage required for transistor behavior at 90-95% of a monolayer composed of standing molecules. Surface sputtering and an increased sample temperature during epindolidione deposition augmented the surface diffusion of adsorbing molecules and therefore led to a lower number of better-ordered islands. Consequently, while the onset of charge transport was delayed, higher saturation mobility was obtained. The highest, bottom-contact configuration, mobilities of approximately 2.5 × 10-3cm2/Vs were found for high coverages (50 nm) on sputtered samples. The coverage dependence of the mobility showed very different characteristics for the different gate dielectrics, while the change of the threshold voltage with coverage was approximately the same for all systems. An apparent decrease of the mobility with increasing coverage on the less polar PNDPE was attributed to a change in molecular orientation from upright standing in the thin-film phase to tilted in the bulk phase. From temperature-dependent mobility measurements we calculated activation barriers for the charge transport between 110 meV and 160 meV, depending on the dielectric configuration.

Functional corannulene: diverse structures, enhanced charge transport, and tunable optoelectronic properties.

Chemical functionalization of various hydrocarbons, such as coronene, corannulene, and so forth, shows good promise in electronics applications because of their tunable optoelectronic properties. By using quantum chemical calculations, we have investigated the changes in the corannulene buckybowl structure, which greatly affect its electronic and optical properties when functionalized with different electron-withdrawing imide groups. We find that the chemical nature and position of functional groups strongly regulate the stacking geometry, π-stacking interactions, and electronic structure. Herein, a range of optoelectronic properties and structure-property relationships of various imide-functionalized corannulenes are explored and rationalized in detail. In terms of carrier mobility, we find that the functionalization strongly affects the reorganization energy of corannulene, while the enhanced stacking improves hopping integrals, favoring the carrier mobility of crystals of pentafluorophenylcorannulene-5-monoimide. The study shows a host of emerging optoelectronic properties and enhancements in the charge-transport characteristics of functionalized corannulene, which may find possible semiconductor and electronics applications.

On the importance of crystal structures for organic thin film transistors.

Historically, knowledge of the molecular packing within the crystal structures of organic semiconductors has been instrumental in understanding their solid-state electronic properties. Nowadays, crystal structures are thus becoming increasingly important for enabling engineering properties, understanding polymorphism in bulk and in thin films, exploring dynamics and elucidating phase-transition mechanisms. This review article introduces the most salient and recent results of the field.