Transport In Field-effect Transistors Research Articles

Achieving Ideal and Environmentally Stable n-Type Charge Transport in Polymer Field-Effect Transistors.

Realizing ideal charge transport in field-effect transistors (FETs) of conjugated polymers is crucial for evaluating device performance, such as carrier mobility and practical applications of conjugated polymers. However, the current FETs using conjugated polymers as the active layers generally show certain non-ideal transport characteristics and poor stability. Here, ideal charge transport of n-type polymer FETs is achieved on flexible polyimide substrates by using an organic-inorganic hybrid double-layer dielectric. Deposited conjugated polymer films show highly ordered structures and low disorder, which are supported by grazing-incidence wide-angle X-ray scattering, near-edge X-ray absorption fine structure, and molecular dynamics simulations. Furthermore, the organic-inorganic hybrid double-layer dielectric provides low interfacial defects, leading to excellent charge transport in FETs with high electron mobility (1.49 ± 0.46 cm2V-1s-1) and ideal reliability factors (102 ± 7%). Fabricated polymer FETs show a self-encapsulation effect, resulting in high stability of the FET charge transport. The polymer FETs still work with high mobility above 1 cm2V-1s-1 after storage in air for more than 300 days. Compared with state-of-the-art conjugated polymer FETs, this work simultaneously achieves ideal charge transport and environmental stability in n-type polymer FETs, facilitating rapid device optimization of high-performance polymer electronics.

Modification of Two-Dimensional Tin-Based Perovskites by Pentanoic Acid for Improved Performance of Field-Effect Transistors.

Understanding and controlling the nucleation and crystallization in solution-processed perovskite thin films are critical to achieving high in-plane charge carrier transport in field-effect transistors (FETs). This work demonstrates a simple and effective additive engineering strategy using pentanoic acid (PA). Here, PA is introduced to both modulate the crystallization process and improve the charge carrier transport in 2D 2-thiopheneethylammonium tin iodide ((TEA)2 SnI4 ) perovskite FETs. It is revealed that the carboxylic group of PA is strongly coordinated to the spacer cation TEAI and [SnI6 ]4- framework in the perovskite precursor solution, inducing heterogeneous nucleation and lowering undesired oxidation of Sn2+ during the film formation. These factors contribute to a reduced defect density and improved film morphology, including lower surface roughness and larger grain size, resulting in overall enhanced transistor performance. The reduced defect density and decreased ion migration lead to a higher p-channel charge carrier mobility of 0.7 cm2 V-1 s-1 , which is more than a threefold increase compared with the control device. Temperature-dependent charge transport studies demonstrate a mobility of 2.3 cm2 V-1 s-1 at 100 K due to the diminished ion mobility at low temperatures. This result illustrates that the additive strategy bears great potential to realize high-performance Sn-based perovskite FETs.

Role of oxygen within end group substituents on film morphology and charge carrier transport in thiophene/phenylene small-molecule semiconductors

In this study, the end group polarity of (5,5′)-biphenyl-(2,2’)-bithiophenes (PTTPs) was systematically varied from alkyl (1) to alkoxy (2) with one oxygen atom to glycol (3) with two oxygen atoms while the overall length of the end groups is kept constant. Thin films of the three compounds were sublimated at different substrate temperatures and their morphology, crystallinity and charge carrier transport in field-effect transistors was investigated to draw structure-property relationships for the PTTP derivatives. For all three compounds, the effective charge carrier mobility is improved with higher substrate temperatures at which films with higher crystallinity and larger grains are formed. The effective mobility decreases with higher polarity of the end groups from alkyl to alkoxy and glycol. The reliability factor of the alkyl (1) and alkoxy (2) substituted PTTPs decreases with higher substrate temperature, but at the same time this value is enhanced for the glycol substituted molecules (3). The transistors of 3 prepared at higher substrate temperatures also show a reduced threshold voltage and smaller hysteresis in the transfer characteristics. These insights are important for the understanding of the impact of oxygen incorporation into side chain/end group substituents of organic semiconductors and their implementation in organic electrochemical transistors, thermoelectrics and photovoltaics.

Relation between Spherulitic Growth, Molecular Organization, and Charge Carrier Transport in Meniscus‐Guided Coated Organic Semiconducting Films (Adv. Electron. Mater. 8/2021)

Meniscus-Guided Coating Tomasz Marszalek, Wojciech Pisula, and colleagues show how the size and orientation of spherulitic domains of a molecular semiconductor are controlled by the deposition velocity during meniscus-guided coating in article number 2100397. By tuning the thin film morphology into large domains, the charge carrier transport in field-effect transistors is improved.

Switching from Electron to Hole Transport in Solution-Processed Organic Blend Field-Effect Transistors.

Organic electronics became an attractive alternative for practical applications in complementary logic circuits due to the unique features of organic semiconductors such as solution processability and ease of large-area manufacturing. Bulk heterojunctions (BHJ), consisting of a blend of two organic semiconductors of different electronic affinities, allow fabrication of a broad range of devices such as light-emitting transistors, light-emitting diodes, photovoltaics, photodetectors, ambipolar transistors and sensors. In this work, the charge carrier transport of BHJ films in field-effect transistors is switched from electron to hole domination upon processing and post-treatment. Low molecular weight n-type N,N′-bis(n-octyl)-(1,7&1,6)-dicyanoperylene-3,4:9,10-bis(dicarboximide) (PDI8-CN2) was blended with p-type poly[2,5-bis(3-tetradecylthiophene-2-yl)thieno[3,2-b]thiophene] (PBTTT-C14) and deposited by spin-coating to form BHJ films. Systematic investigation of the role of rotation speed, solution temperature, and thermal annealing on thin film morphology was performed using atomic force microscopy, scanning electron microscopy, and grazing incidence wide-angle X-ray scattering. It has been determined that upon thermal annealing the BHJ morphology is modified from small interconnected PDI8-CN2 crystals uniformly distributed in the polymer fraction to large planar PDI8-CN2 crystal domains on top of the blend film, leading to the switch from electron to hole transport in field-effect transistors.

PHYSICS OF NANOTRANSISTORS: 2D MOS ELECTROSTATICS AND VIRTUAL SOURCE MODEL

In the fourth one from the line our new tutorial reviews, directed to serve students, university teachers and researchers, the 2D electrostatics of MOS is considered in detail. It is demonstrated, that 2D electrostatics degrades electron transport in field effect transistors by increasing the subthreshold swing and causing the DIBL effect, which in its turn increases the output conductivity and reduces the threshold voltage in short-channel transistors. Since these effects are more pronounced in short-channel transistors, they are also called short channel effects. As transistors get smaller and smaller, the main challenge with circuitry is to control the short-channel effects. As a rule, numerical modeling is required.

Charge Transport in Mixed Semiconducting Carbon Nanotube Networks with Tailored Mixing Ratios.

The ability to prepare uniform and dense networks of purely semiconducting single-walled carbon nanotubes (SWNTs) has enabled the design of various (opto-)electronic devices, especially field-effect transistors (FETs) with high carrier mobilities. Further optimization of these SWNT networks is desired to surpass established solution-processable semiconductors. The average diameter and diameter distribution of nanotubes in a dense network were found to influence the overall charge carrier mobility; e.g., networks with a broad range of SWNT diameters show inferior transport properties. Here, we investigate charge transport in FETs with nanotube networks comprising polymer-sorted small diameter (6,5) SWNTs (0.76 nm) and large diameter plasma torch SWNTs (1.17-1.55 nm) in defined mixing ratios. All transistors show balanced ambipolar transport with high on/off current ratios and negligible hysteresis. While the range of bandgaps in these networks creates a highly uneven energy landscape for charge carrier hopping, the extracted hole and electron mobilities vary nonlinearly with the network composition from the lowest mobility (15 cm2 V-1 s-1) for only (6,5) SWNT to the highest mobility (30 cm2 V-1 s-1) for only plasma torch SWNTs. A comparison to numerically simulated network mobilities shows that a superposition of thermally activated hopping across SWNT-SWNT junctions and diameter-dependent intratube transport is required to reproduce the experimental data. These results also emphasize the need for monochiral large diameter nanotubes for maximum carrier mobilities in random networks.

Organic Heterojunctions Formed by Interfacing Two Single Crystals from a Mixed Solution.

Organic heterojunctions are widely used in organic electronics and they are composed of semiconductors interfaced together. Good ordering in the molecular packing inside the heterojunctions is highly desired but it is still challenging to interface organic single crystals to form single-crystalline heterojunctions. Here, we describe how organic heterojunctions are formed by interfacing two single crystals from a droplet of a mixed solution containing two semiconductors. Based on crystallization of six organic semiconductors from a droplet on a substrate, two distinct crystallization mechanisms have been recognized in the sense that crystals form at either the top interface between the air and solution or the bottom interface between the substrate and solution. The preference for one interface rather than the other depends on the semiconductor-substrate pair and, for a given semiconductor, it can be switched by changing the substrate, suggesting that the preference is associated with the semiconductor-substrate molecular interaction. Furthermore, simultaneous crystallization of two semiconductors at two different interfaces to reduce their mutual disturbance results in the formation of bilayer single crystals interfaced together for organic heterojunctions. These single-crystalline heterojunctions exhibit ambipolar charge transport in field-effect transistors, with the highest electron mobility of 1.90 cm2 V-1 s-1 and the highest hole mobility of 1.02 cm2 V-1 s-1. Hence, by elucidating the interfacial crystallization events, this work should greatly harvest the solution-grown organic single-crystalline heterojunctions.

Temperature dependent carrier mobility in organic field-effect transistors: The role of dielectrics

It has been shown that the use of a ferroelectric dielectric in 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) field-effect transistors (FETs) results in a negative coefficient of carrier mobility, a signature of a band-like transport, above a certain temperature [A. Laudari and S. Guha, Phys. Rev. Appl. 6, 044007 (2016)]. Along with spontaneous polarization, polymer ferroelectric dielectrics offer a platform for tuning interfacial transport in FETs as their dielectric constant may vary nearly by an order of magnitude with temperature. In this work, we explore a variety of organic and inorganic dielectrics with varying dielectric constants on the temperature-dependent transport properties of TIPS-pentacene organic FETs to obtain a comprehensive insight into the role of energetic disorder and trap states. In particular, a high κ dielectric, Al2O3, shows an activated transport throughout the temperature regime, whereas the ferroelectric copolymer poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE), with comparable and even higher values of κ compared to Al2O3, above 200 K shows a very different behavior. Additionally, the external poling condition of the PVDF-TrFE dielectric plays a role. We attribute the band-like negative coefficient of carrier mobility, observed at high temperatures, in TIPS-pentacene FETs with unpoled PVDF-TrFE to a polarization fluctuation process and explore this phenomenon using the concept of transport energy.

Alkyne Benzannulation Reactions for the Synthesis of Novel Aromatic Architectures.

Aromatic compounds and polymers are integrated into organic field effect transistors, light-emitting diodes, photovoltaic devices, and redox-flow batteries. These compounds and materials feature increasingly complex designs, and substituents influence energy levels, bandgaps, solution conformation, and crystal packing, all of which impact performance. However, many polycyclic aromatic hydrocarbons of interest are difficult to prepare because their substitution patterns lie outside the scope of current synthetic methods, as strategies for functionalizing benzene are often unselective when applied to naphthalene or larger systems. For example, cross-coupling and nucleophilic aromatic substitution reactions rely on prefunctionalized arenes, and even directed metalation methods most often modify positions near Lewis basic sites. Similarly, electrophilic aromatic substitutions access single regioisomers under substrate control. Cycloadditions provide a convergent route to densely functionalized aromatic compounds that compliment the above methods. After surveying cycloaddition reactions that might be used to modify the conjugated backbone of poly(phenylene ethynylene)s, we discovered that the Asao-Yamamoto benzannulation reaction is notably efficient. Although this reaction had been reported a decade earlier, its scope and usefulness for synthesizing complex aromatic systems had been under-recognized. This benzannulation reaction combines substituted 2-(phenylethynyl)benzaldehydes and substituted alkynes to form 2,3-substituted naphthalenes. The reaction tolerates a variety of sterically congested alkynes, making it well-suited for accessing poly- and oligo(ortho-arylene)s and contorted hexabenzocoronenes. In many cases in which asymmetric benzaldehyde and alkyne cycloaddition partners are used, the reaction is regiospecific based on the electronic character of the alkyne substrate. Recognizing these desirable features, we broadened the substrate scope to include silyl- and halogen-substituted alkynes. Through a combined experimental and computational approach, we have elucidated mechanistic insight and key principles that govern the regioselectivity outcome of the benzannulation of structurally diverse alkynes. We have applied these methods to prepare sterically hindered, shape-persistent aromatic systems, heterocyclic aromatic compounds, functionalized 2-aryne precursors, polyheterohalogenated naphthalenes, ortho-arylene foldamers, and graphene nanoribbons. As a result of these new synthetic avenues, aromatic structures with interesting properties were uncovered such as ambipolar charge transport in field effect transistors based on our graphene nanoribbons, conformational aspects of ortho-arylene architectures resulting from intramolecular π-stacking, and modulation of frontier molecular orbitals via protonation of heteroatom containing aromatic systems. Given the availability of many substituted 2-(phenylethynyl)benzaldehydes and the regioselectivity of the benzannulation reaction, naphthalenes can be prepared with control of the substitution pattern at seven of the eight substitutable positions. Researchers in a range of fields are likely to benefit directly from newly accessible molecular and polymeric systems derived from polyfunctionalized naphthalenes.

Anomalous Ambipolar Transport of Organic Semiconducting Crystals via Control of Molecular Packing Structures.

Organic crystals deposited on 2-dimensional (2D) van der Waals substrates have been widely investigated due to their unprecedented crystal structures and electrical properties. van der Waals interaction between organic molecules and the substrate induces epitaxial growth of high quality organic crystals and their anomalous crystal morphologies. Here, we report on unique ambipolar charge transport of a "lying-down" pentacene crystal grown on a 2D hexagonal boron nitride van der Waals substrate. From in-depth analysis on crystal growth behavior and ultraviolet photoemission spectroscopy measurement, it is revealed that the pentacene crystal at the initial growth stage have a lattice-strained packing structure and unique energy band structure with a deep highest occupied molecular orbital level compared to conventional "standing-up" crystals. The lattice-strained pentacene few layers enable ambipolar charge transport in field-effect transistors with balanced hole and electron field-effect mobilities. Complementary logic circuits composed of the two identical transistors show clear inverting functionality with a high gain up to 15. The interesting crystal morphology of organic crystals on van der Waals substrates is expected to attract broad attentions on organic/2D interfaces for their electronic applications.

Effect of capping group on the properties of non-polymeric diketopyrrolopyrroles for solution-processed bulk heterojunction solar cells

Abstract Solution-processable non-polymeric organic semiconductors are attractive for opto-electronic applications due to their relatively simple synthetic reproducibility and characterization, and enhanced capability for fine-tuning of their properties. We report the synthesis, charge transport, photophysics, and photovoltaic properties of three non-polymeric materials based upon bisarylthiophenyl diketopyrrolopyrrole [DPP(ThAr)2]. The DPP(ThAr)2 molecules are comprised of solubilizing alkyl groups, 2-ethylhexyl (for 1a) and 2-octyldodecyl (for 1b and 2), which are capped with electron accepting moieties - fluorenone (1) or benzothiadiazole (2). While the materials could be prepared under standard Suzuki-Miyaura cross-coupling conditions, a simple direct arylation afforded 2 and 1b in good yields. We found 1a with a short alkyl chain lacked sufficient solubility for solution processing but 1b and 2 are solution processable and form good quality films. All three materials exhibited ambipolar charge transport in field effect transistors, with 1b showing balanced charge mobilities of about 10−3 cm2 V−1 s−1. Bulk heterojunction solar cells of 1b or 2 with PC71BM were found to have high open-circuit voltages (up to 0.9 V) with power conversion efficiencies of up to 4.5% and 2.6%, respectively.

From bidirectional rectifier to polarity-controllable transistor in black phosphorus by dual gate modulation

In complementary metal oxide semiconductor (CMOS) technology, well-defined unipolar transport in field-effect transistors (FETs) is a basic requirement for logic operations, which can be realized by controllable doping of the semiconductor with electrons (n-type) or holes (p-type). However, recent demonstration of polarity controllable transistors in 2D semiconductors provides a flexible way in circuit design with increased circuit integration density. Here we demonstrate the conversion of a bidirectional rectifier to a polarity-controllable transistor in black phosphorus (BP) by dual gate modulation. Electrical characterization of the BP bidirectional rectifier reveals a current rectification of ~35 at room temperature that increases to ~350 upon lowering the temperature to 110 K. Employing cross-linked PMMA as a top gate and combining it together with the global back gate of the SiO2 substrate, well-defined unipolar transport (n- or p-type) in BP could get accessed. This successful realization of polarity-controllable transistor in BP provides an alternative design for development of BP logic electronics.

Gate-voltage-dependent charge transport in multi-dispersed polymer thin films

In semiconductor polymers, charge transport usually occurs via hopping between localized states, which are generally multi-dispersed due to multi-dispersed chemical structures, crystallinities, and phase segregations. We report a combined modeling and experimental study to investigate gate-voltage-dependent charge transport in field-effect transistors based on multi-dispersed polymers including semiconductor:semiconductor and semiconductor:insulator blends. Film-depth-dependent charge accumulation and transport are correlated with vertical composition profiles and film-depth-dependent energetic distribution of localized states. Even low gate-voltage could accumulate charges in any depth of the films, greatly increasing charge density in some (sub-) components for effective charge transport. Therefore, neither overall high crystallinity nor molecular ordering near the semiconductor-dielectric interface is necessarily required for high field-effect mobility (μFET). This study not only proposes a model for high effective μFET recently reported in some nearly amorphous polymer films and the “bislope feature” in their transfer characteristics but also helps improve transistor performances and exploit transistor operations via manipulating charge distribution in multi-dispersed films.

Side-Chain-Induced Rigid Backbone Organization of Polymer Semiconductors through Semifluoroalkyl Side Chains.

While high-mobility p-type conjugated polymers have been widely reported, high-mobility n-type conjugated polymers are still rare. In the present work, we designed semifluorinated alkyl side chains and introduced them into naphthalene diimide-based polymers (PNDIF-T2 and PNDIF-TVT). We found that the strong self-organization of these side chains induced a high degree of order in the attached polymer backbones by forming a superstructure composed of "backbone crystals" and "side-chain crystals". This phenomenon was shown to greatly enhance the ordering along the backbone direction, and the resulting polymers thus exhibited unipolar n-channel transport in field-effect transistors with remarkably high electron mobility values of up to 6.50 cm(2) V(-1) s(-1) and with a high on-off current ratio of 10(5).

Effects of PNDIT2 end groups on aggregation, thin film structure, alignment and electron transport in field-effect transistors

End group control: PNDIT2 with OH and tolyl chain termini are made and comparatively investigated.

(Invited) Effect of Individual Dopants in Nano-SOI-MOSFETs and Nano-pn-Diodes

Recently, individual dopant atoms have been utilized as naturally-created quantum dots (QDs) that allow the control of single-carrier tunneling transport in field-effect transistors (FETs), typically at low temperatures. It has been also reported that a few coupled-dopants can form a relatively larger and more complex QD, which may be, however, more practical than a single-dopant QD in terms of fabrication processes and/or elevated-temperature operation. Such discreteness of dopants in nanostructures, down to the level of individuality of dopants, has been observed not only in FETs, but also in nanoscale pn-diodes. Here, we outline results of single-electron tunneling transport via donors in FETs in the regime of low concentration (individual donors) and high concentration (clustered or coupled donors). We also show basic results of current enhancement in low-dimensional Esaki diodes due to tunneling through dopants. Finally, observation of dopant potentials by Kelvin probe force microscopy is described.

High-Mobility n-Type Conjugated Polymers Based on Electron-Deficient Tetraazabenzodifluoranthene Diimide for Organic Electronics

High-mobility p-type and ambipolar conjugated polymers have been widely reported. However, high-mobility n-type conjugated polymers are still rare. Herein we present poly(tetraazabenzodifluoranthene diimide)s, PBFI-T and PBFI-BT, which exhibit a novel two-dimensional (2D) π-conjugation along the main chain and in the lateral direction, leading to high-mobility unipolar n-channel transport in field-effect transistors. The n-type polymers exhibit electron mobilities of up to 0.30 cm(2)/(V s), which is among the highest values for unipolar n-type conjugated polymers. Complementary inverters incorporating n-channel PBFI-T transistors produced nearly perfect switching characteristics with a high gain of 107.

TIPS-pentacene crystalline thin film growth

The crystalline film growth of TIPS-pentacene thin films by confined solution deposition is investigated. The crystalline thin films grow dendritic in the initial stage and continue to grow to elongated plate-like crystals when the solution is deposited in a confined space in-plane. The majority of the thin film, containing smaller thin crystals, is formed within the first 10s after depositing the solution and continues to grow in minutes to millimeter sized single crystals. By atomic force microscopy we show that impurities are expelled by the growing crystals and clusters accumulate at step edges on the surface of the larger crystals. The influence of crystal thickness and orientation on the electronic transport in field-effect transistors is studied, and shows an optimum performance for devices with thin elongated crystals that are aligned parallel to the electric field between the source–drain electrodes.

Theoretical Evaluation of Ballistic Electron Transport in Field-Effect Transistors with Semiconducting Graphene Channels

In this paper, we present a theoretical evaluation of ballistic electron transport in field-effect transistors (FETs) with semiconducting graphehe channels; bilayer graphenes (BLGs), monolayer graphene nanoribbons (MLGNRs), and bilayer graphene nanoribbons (BLGNRs). We found that the use of BLGNRs produces little advantage in either increasing the band gap energy or improving the device performance, as compared with a pristine BLG device. We also demonstrated that BLG-based FETs exhibit quite different behavior in the drain current versus gate voltage characteristics from that of MLGNR-FETs, since a distorted dispersion relation around the conduction band minima significantly affects the drain current property.