Field Effect Transistor Applications Research Articles

Experimental Realization of Monolayer α-Tellurene.

2D materials emerge as a versatile platform for developing next-generation devices. The experimental realization of novel artificial 2D atomic crystals, which does not have bulk counterparts in nature, is still challenging and always requires new physical or chemical processes. Monolayer α-tellurene is predicted to be a stable 2D allotrope of tellurium (Te), which has great potential for applications in high-performance field-effect transistors. However, the synthesis of monolayer α-tellurene remains elusive because of its complex lattice configuration, in which the Te atoms are stacked in tri-layers in an octahedral fashion. Here, a self-assemble approach, using three atom-long Te chains derived from the dynamic non-equilibrium growth of an a-Si:Te alloy as building blocks, is reported for the epitaxial growth of monolayer α-tellurene on a Sb2 Te3 substrate. By combining scanning tunneling microscopy/spectroscopy with density functional theory calculations, the surface morphology and electronic structure of monolayer α-tellurene are revealed and the underlying growth mechanism is determined. The successful synthesis of monolayer α-tellurene opens up the possibility for the application of this new single-element 2D material in advanced electronic devices.

Enhanced visible-light-driven photocatalytic activity in SiPGaS/arsenene-based van der Waals heterostructures

Van der Waals heterostructures (vdWHs) showcase robust and tunable light-matter interactions, establishing an intriguing realm for investigating atomic-scale photocatalytic properties. Here, we employ ab initio methods to study the photocatalytic and optical properties of semiconducting SiPGaS/arsenene-based vdWHs with a type-II band alignment. Across the heterointerfaces, there exists significant built-in electric fields and large potential drop, in turn facilitating the spatial separation of photo-generated electron-hole pairs. These vdWHs further possess high carrier mobility in the order of 102 cm2V⁻1S⁻1, which combining with appropriate band edge positions, endow the vdWHs an absorption coefficient of ∼10⁵ cm⁻1 to harvest a maximal portion of the solar spectrum for visible-light-driven photocatalytic applications. Our findings also reveal transition of the type-II band alignment in a type-III configuration via compressive strain for tunneling field-effect transistor application. Furthermore, both types of vdWHs exhibit enhanced suitability for photocatalysis under conditions with a pH of 2.

Chalcogenopheno[3,2-b]pyrrole-Containing Donor-Acceptor-Donor Organic Semiconducting Small Molecules for Organic Field-Effect Transistors.

A group of chalcogenopheno[3,2-b]pyrroles, including thieno[3,2-b]pyrrole (TP), furo[3,2-b]pyrrole (FP), and selenopheno[3,2-b]pyrrole (SeP), and thieno[3,2-b]thiophene (TT) electron-donating units were coupled with a thiophene-flanked diketopyrrolo[3,4-c]pyrrole (ThDPP) acceptor to generate four donor-acceptor-donor (D-A-D) semiconducting small molecules (ThDPP-TT, ThDPP-FP, ThDPP-TP, and ThDPP-SeP). This study systematically investigated the differences between chalcogenopheno[3,2-b]pyrroles and TT. From the characterizations, chalcogenopheno[3,2-b]pyrrole-containing molecules showed lower band gaps and binding-energy cold crystallization behavior. The enthalpies of cold crystallization were correlated with the weight of the chalcogen in ThDPP-FP, ThDPP-TP, and ThDPP-SeP, which were evaluated as intermolecular chalcogen-bond interactions between chalcogen and pyrrole nitrogen in chalcogenopheno[3,2-b]pyrroles. A stronger chalcogen bond interaction resulted in stronger self-aggregation in thin films with thermal treatment, which resulted in a polycrystalline structure in chalcogenopheno[3,2-b]pyrrole-containing molecules. For the application in an organic field-effect transistor, all four molecules showed good performance with the highest hole mobilities as 6.33 × 10-3 cm2 V-1 s-1 for ThDPP-TT, 2.08 × 10-2 cm2 V-1 s-1 for ThDPP-FP, 1.87 × 10-2 cm2 V-1 s-1 for ThDPP-TP, and 6.32 × 10-3 cm2 V-1 s-1 for ThDPP-SeP, and the change of mobility is well correlated to the root-mean-square roughness of the thin films. Overall, all the chalcogenopheno[3,2-b]pyrrole-containing molecules showed lower band gaps, polymorphism, and better charge transport properties compared to TT-containing molecules, which motivates replacing TT with chalcogenopheno[3,2-b]pyrroles in conjugated polymers, non-fullerene small molecular acceptors, and narrow-band-gap donors.

Intrinsic Ferromagnetic Semiconductors with High Saturation Magnetization from Hybrid Perovskites.

Ferromagnetic semiconductors (FMS) enable simultaneous control of both charge and spin transport of charge carriers, which have emerged as a class of highly desirable but rare material for applications in spin field-effect transistors and quantum computing. Organic-inorganic hybrid perovskite with high compositional adjustability and structural versatility can offer unique benefits in the design of FMS but has not been fully explored. Here we demonstrate a series of molecular FMSs based on two-dimensional organic-inorganic hybrid perovskite structure, namely (2ampy)CuCl4 , (3ampy)CuCl4 and (4ampy)CuCl4 , which exhibits high saturation magnetization, dramatic temperature-dependent conductivity change and tunable ferromagnetic resonance. Magnetic measurements revealed high saturation magnetization up to 18.56 emu/g for (4ampy)CuCl4 , which is one of the highest value among reported hybrid FMSs to date. Conductivity studies of the three FMSs demonstrate that the smaller adjacent octahedron distance in the two-dimensional layer results in higher conductivity. Systematic ferromagnetic resonance investigation shows that the gyromagnetic ratio and Landau factor values are strongly dependent on the types of organic cations used. This work demonstrates that two-dimensional hybrid perovskite materials can simultaneously possess both tunable long-range ferromagnetic ordering and semiconductivity, providing a straightforward strategy for designing and synthesizing high-performance intrinsic FMSs. This article is protected by copyright. All rights reserved.

Effect of fluoride layer thickness on the leakage current in Au/CaF2/Si(111) heterostructures

Thin films of calcium fluoride with a nominal thickness from 2 up to 20 nm were grown on silicon-(111) surface by means of molecular beam epitaxy. The interest to fluorite insulating films is stipulated by the potential applications in field-effect transistors with a 2D channel. The studied Au/CaF2/Si heterostructures exhibited behavior which is typical for a metal-insulator-semiconductor system. In order to attain a quantitative agreement between the measured current–voltage curves and the theoretical model, spatial fluctuations of the fluoride layer thickness had to be accounted for. The standard deviation of the CaF2 layer thickness was found to be between 0.2 and 1.2 nm tending to increase with the nominal thickness. These values are in agreement with root mean square surface roughness measured by atomic force microscopy. A satisfactory reproducibility of the electric characteristics of the studied films makes CaF2 a promising insulating material for electronic devices.

Donor-Acceptor-Based Organic Polymer Semiconductor Materials to Achieve High Hole Mobility in Organic Field-Effect Transistors.

Organic polymer semiconductor materials are conveniently tuned to energy levels because of their good chemically modifiable properties, thus enhancing their carrier transport capabilities. Here, we have designed and prepared a polymer with a donor-acceptor structure and tested its potential as a p-type material for organic field-effect transistor (OFET) applications using a solution-processing method. The conjugated polymers, obtained via the polymerization of the two monomers relying on the Stille coupling reaction, possess extremely high molecular weights and thermodynamic stability. Theoretical-based calculations show that PDPP-2S-Se has superior planarity, which is favorable for carrier transport within the main chain. Photophysical and electrochemical measurements systematically investigated the properties of the material and the energy levels with respect to the theoretical values. The maximum hole mobility of the PDPP-2S-Se-based OFET device is 0.59 cm2 V-1 s-1, which makes it a useful material for potential organic electronics applications.

Fermi level depinning via insertion of a graphene buffer layer at the gold–2D tin monoxide contact

Two-dimensional (2D) tin monoxide (SnO) has attracted much attention owing to its distinctive electronic and optical properties, which render itself suitable as a channel material in field effect transistors (FETs). However, upon contact with metals for such applications, the Fermi level pinning effect may occur, where states are induced in its band gap by the metal, hindering its intrinsic semiconducting properties. We propose the insertion of graphene at the contact interface to alleviate the metal-induced gap states. By using gold (Au) as the electrode material and monolayer SnO (mSnO) as the channel material, the geometry, bonding strength, charge transfer and tunnel barriers of charges, and electronic properties including the work function, band structure, density of states, and Schottky barriers are thoroughly investigated using first-principles calculations for the structures with and without graphene to reveal the contact behaviours and Fermi level depinning mechanism. It has been demonstrated that strong covalent bonding is formed between gold and mSnO, while the graphene interlayer forms weak van der Waals interaction with both materials, which minimises the perturbance to the band structure of mSnO. The effects of out-of-plane compression are also analysed to assess the performance of the contact under mechanical deformation, and a feasible fabrication route for the heterostructure with graphene is proposed. This work systematically explores the properties of the Au–mSnO contact for applications in FETs and provides thorough guidance for future exploitation of 2D materials in various electronic applications and for selection of buffer layers to improve metal–semiconductor contact.

Back Gate Bias Influence on BESOI ISFET Sensitivity

The application of Field Effect Transistors (FETs) to sensors and biosensors allows a mass production, low cost, small size, fast response and, also, the possibility of integrating the device and conditioning signal circuit in the same integrated circuit (IC). The Ion Sensitive Field Effect Transistor (ISFET), invented in 1970 by Piet Bergveld (1), is a device similar to the conventional Metal-Oxide-Semiconductor Field Effect Transistor (MOSFET), except that the metal gate is replaced by an inert electrode/pseudo electrode and a sample solution, in order to expose the gate oxide layer to ions present in the solution. The solution charges change the electrical potential in the gate oxide surface and, consequently, the device threshold voltage changes as a function of the ion concentration in the sample solution, being used as a pH sensor. Thus, the ISFET is a very promising device to Point-of-Care (POC) monitoring, such as COVID-19 control (2) and for continuous in vivo monitoring ion activity in biological processes (3)-(6).The BESOI (Back Enhanced Silicon-On-Insulator) MOSFET is a device patented in 2015 by João Antonio Martino and Ricardo Cardoso Rangel (7). This device is easy to fabricate and low cost. In the last years, the research using this device as a sensor/biosensor has been done (8)-(14). This paper presents, for the first time, the BESOI MOSFET working as an Ion Sensitive Field Effect Transistor (ISFET): the BESOI ISFET. Therefore, the focus of this work is to study the device electrical behavior influenced for pH standard solutions.The BESOI ISFET was fabricated at Integrated System Laboratory (LSI) from University of Sao Paulo (USP), Brazil. It is a planar device made on a SOI (Silicon-On-Insulator) wafer with three conventional photolithography steps, in an analogous way to previous work (15) and one more photolithography step to create microchannel and microreservoirs with SU-8 (16) layer to contain the sample solution. The wafer has no doping process (there is only the natural wafer doping of 1015 cm-3). The silicon channel layer and the gate oxide (SiO2) thicknesses are 10 nm and 25 nm, respectively. The buried oxide layer thickness is 200 nm. The drain and source contacts are fabricated with nickel and the contact pads using aluminum. The Figure 1 presents the final device layout and the Figure 2 shows the device schematic drawn.Differently from a conventional ISFET, where the drain current flows at the front interface, in the BESOI ISFET the drain current flows at the back interface. As the BESOI ISFET is a non-intentionally doped device, the free conduction charge layer is formed by biasing the Back Gate electrode (VGB). When a positive enough VGB is applied, electrons are attracted and accumulated at the back interface, and therefore, current flows from source to drain when VDS (Drain bias) is applied. A Platinum (Pt) pseudo-electrode is used to apply front-gate voltage (VGF) to the sample solution.The experimental drain current (IDS) as a function of the front-gate voltage (VGF), for 25 V applied at the back-gate (VGB), is presented in Figure 3.A, which is possible to observe that the neutral pH (pH7) curve stayed between the acid pH (pH4) curve, in the left, and alkaline pH (pH10) curve, in the right. This result shows that the threshold voltage (VTH) is lower for acid pH and higher for alkaline pH, what is compatible with the conventional ISFET results present in the literature (17). To corroborate the experimental measurement result, the device simulation was made with TCAD-Sentaurus (18), based in the paper (19). Figure 3.B shows the same trend for the simulated device with pH solution for any VGB value.In Figure 4, the threshold voltage was analyzed as a function of the pH for different VGB values. The VTH increases (becomes more positive) for alkaline pH values, regardless of the VGB applied. However, the VTH variation in the pH range, between pH4 and pH10, is different for different VGB values. With higher VGB applied, higher is the VTH variation. In Figure 5 Is possible to see clearly that the sensitivity (ΔVTH /ΔpH) increases with the VGB increase probably due to the small influence of the series resistance. In another hand, the acquired sensitivity values for VGB higher than 15 V in this work (about 25-33 mV/pH, approximately), is compatible with results present in the literature for conventional ISFETs with silicon dioxide (SiO2) for gate insulator (20). Figure 1

Electrochemistry of Polyfluorinated Organic Molecules in Nonaqueous Electrolyte Solutions

Fluoroorganic molecules provide significant benefit for many applications including pharmaceuticals, agrichemicals, and advanced functional materials due to its highly stable carbon fluorine bonds. Fluorination can have profound effects upon tuning the electronic and optical properties of organic molecules. Thus, fluorine is found in many state-of-the-art materials. For example, fluorinated liquid crystals are used for active-matrix liquid crystal displays; fluorinated membranes are utilized as proton transfer elements necessary for the function of fuel cells; fluorinated electrolyte solutions are tested in lithium batteries to improve their long-term stability and cell voltage. Lately, fluorinated and perfluoroalkylated organic semiconductors were reported for its application in organic field effect transistors (OFETs). Fluorination can tune a p-type organic semiconductor into an n-type semiconductor because of the strong electron withdrawing effect of fluorine, though use of multiple fluorine substituents directly on the aromatics or use of trifluoromethyl and perfluoroalkyl substituents on the pi system is essential for such conversion.The high electronegativity of fluorine results in exceptionally strong bonds to carbon (BDE = 110-126 kcal/mol). Moreover, fluorine substitution results in an increase in the C-C bond energy in fluorocarbons. Strong C-F and corresponding strong C-C bonds in fluorocarbons make them less polarizable than typical hydrocarbons. The highly polar, weakly polarizable, non-hydrogen bonding, non-coordinating properties of perfluoroalkylated materials and perfluoropolyether materials, underlie the motto “Nothing sticks to Teflon® and Teflon®-coated products”. Though all these profound properties of fluoroorganics paved the road for applications exemplified above, their superior stability creates significant challenges for their end-of-life recycling and repurposing, as well as remediation of environmental persistent fluoroorganics such as PFAS. Furthermore, the chemical stability of many these materials often refers to the stability under oxidizing conditions. For fluorinated n-type organic semiconductor materials and fluorinated solvents (e.g. fluoroethylene carbonate) in lithium battery applications, access the stability of these materials and understand its decomposition mechanism under reductive conditions are necessary for rationally optimize the conditions for such applications.In this presentation, we will present and discuss our latest electrochemical study of several different types of polyfluorinated organic molecules involving both fluorinated and perfluoroalkylated aromatics, as well as inert hydrofluorocarbons where only sp3-hybridized carbon presents. As an example, our electrochemical and computational chemistry results indicate that aromatic trifluoromethlation is likely a more stable option against reduction than pentafluoroethylation of the same aromatic core, though the electronic effects of trifluoromethyl and pentafluoroethyl substituents on aromatics are almost identical. We hope that these electrochemical results will shine some lights on searching new materials for electronic and energy storage applications and repurposing inert hydrofluorocarbons, for example, pentafluoroethane, a refrigerant with high global warming potential to be phased out in the next 10-20 years.

Unlocking the Potential of Tin-Based Perovskites: Properties, Progress, and Applications in New-Era Electronics.

Electronics have greatly promoted the development of modern society and the exploration of new semiconducting materials with low cost and high mobility continues to attract interest in the advance of next-generation electronic devices. Among emerging semiconductors, the metal-halide perovskite, especially the nontoxic tin (Sn)-based candidates, has recently made breakthroughs in the field of diverse electronic devices due to its excellent charge transport properties and cost-effective large-area deposition capability at low temperatures. To enable a more comprehensive understanding of this emerging research field and promote the development of new-generation perovskite electronics, this review aims to provide an in-depth understanding with the discussion of unique physical properties of Sn-based perovskites and the summarization of recent research progress of Sn-based perovskite field-effect transistors (FETs) and diverse electronic devices. The unique character of negligible ion migration is also discussed, which is fundamentally different from the lead-based counterparts and provides a great prerequisite for device application. The following section highlights the potential broad applications of Sn-perovskite FETs as a competitive and feasible technology. Finally, an outlook and remaining challenges are given to advance the progression of Sn-based perovskite FETs, especially on the origin and solution of stability problems toward high-performance Sn-based perovskite electronics.

Graphene/Janus ZnO heterostructure to build highly efficient photovoltaic properties

We investigated the effect of F and Cl functionalization of Janus ZnO on the optoelectronic propertiesof Graphene/ZnO (Gra/ZnO) heterojunctions by using Density Functional Theory (DFT). The calculated results show that the Janus ZnO/Gra heterojunction is a van der Waals heterojunction with layer spacing >3 Å for both stacking styles. In addition, the functionalized heterojunction retains the original structure of Gra and has an interface formation energy of <0, making it easy to prepare chemically. Furthermore, different stacking styles can convert heterojunctions from n-type Schottky to ohmic contacts, which has promising applications in field-effect transistors. Moreover, functionalized Janus ZnO/Gra can effectively enhance interlayer charge transfer and improve the transmittance of the heterojunction, which is beneficial for applications in nanoelectronic devices.

Structure-Property Relationship of Macrocycles in Organic Photoelectric Devices: A Comprehensive Review.

Macrocycles have attracted significant attention from academia due to their various applications in organic field-effect transistors, organic light-emitting diodes, organic photovoltaics, and dye-sensitized solar cells. Despite the existence of reports on the application of macrocycles in organic optoelectronic devices, these reports are mainly limited to analyzing the structure-property relationship of a particular type of macrocyclic structure, and a systematic discussion on the structure-property is still lacking. Herein, we conducted a comprehensive analysis of a series of macrocycle structures to identify the key factors that affect the structure-property relationship between macrocycles and their optoelectronic device properties, including energy level structure, structural stability, film-forming property, skeleton rigidity, inherent pore structure, spatial hindrance, exclusion of perturbing end-effects, macrocycle size-dependent effects, and fullerene-like charge transport characteristics. These macrocycles exhibit thin-film and single-crystal hole mobility up to 10 and 26.8 cm2 V-1 s-1, respectively, as well as a unique macrocyclization-induced emission enhancement property. A clear understanding of the structure-property relationship between macrocycles and optoelectronic device performance, as well as the creation of novel macrocycle structures such as organic nanogridarenes, may pave the way for high-performance organic optoelectronic devices.

Aza-anthradithiophene-based conjugated polymers: Synthesis and field-effect transistor application

Acenedithiophenes are classical fused-ring units for constructing conjugated polymers. In this work, a new aza-anthradithiophene unit has been designed and was for the first time employed as building unit to constructing conjugated polymers for organic field-effect transistors. Two conjugated polymers based on thiophthene (P1) and benzothiadiazole (P2) as co-units were synthesized by Stille and Suzuki coupling reactions, respectively. The thermal stability, optical and electrochemical properties, and microstructure were investigated. Organic field-effect transistor devices based on conjugated polymers as semiconductor layer were also fabricated and two polymers exhibited typical hole transport characteristics with the average field-effect mobility up to 7.9 × 10−4 cm2V−1s−1 and Ion/Ioff ratios over 104.

Graphene-based materials and their applications in electrolyte-gated transistors for sensing

Graphene is a two-dimensional material with remarkable physicochemical characteristics. In particular, graphene is highly sensitive to its electronic and electrostatic environment. For these reasons, among various applications of graphene, its use as a sensitive material in field-effect transistors (FETs) is widely studied, especially for biodetection purposes. So, this review aims to introduce the reader to the state of the art of graphene-based materials for their applications in electrolyte-gated graphene field-effect transistors (EGGFETs) for biosensing applications. Among numerous ways to produce graphene-based materials for such devices, some of the most important, widely used methods are presented herein. After that, the working principle of graphene-based FETs is discussed and the various ways to tune graphene's electronic properties are presented. The fabrication methods are discussed, with an emphasis on inkjet printing which allows printing of EGGFETs from aqueous graphene oxide inks, providing that it is subsequently reduced to adjust the mobility of charge carriers and the doping state. Finally, some of the recent works concerning the use of FETs in biosensing applications are reviewed.

Mechanically exfoliated graphene from Sri Lankan vein graphite for field effect transistor application

The Journal of the National Science Foundation of Sri Lanka publishes the results of research in all aspects of Science and Technology. The journal also has a website at http://www.nsf.gov.lk/. 2021 Impact Factor: 0.682The JNSF provides immediate open access to its content on the principle that making research freely available to the public supports a greater global exchange of knowledge.Cover :Leatherback (a), green (b - adult &amp; f - hatchling), hawksbill (c) and olive ridley (d) turtles who nest in Sri Lankan beaches, green turtle crawl marks (e) and by-catch of sea turtles in fisheries (c &amp; d)Photo credits: SJ Perera (a &amp; c), WPN Perera (b &amp; e), K Ekaratne (d &amp; f)

Geometric, Electronic, and Transport Predictions on Two-Dimensional Semiconducting Silicon with Kagome Lattice: Implications for Nanoscale Field-Effect Transistor Applications

Two-dimensional (2D) semiconducting silicon (Si) is significant for the development of micro/nanoelectronics because of their compatibility with the current Si-based technology and the advantages common to 2D electronic materials. Here, by focusing on the kagome lattice (KL), we design a set of semiconducting 2D KL-Si for nanoscale field-effect transistor (FET) applications. First-principles calculations demonstrate that both stable geometric properties and tunable semiconducting electronic properties can be obtained for the 2D KL-Si with different thicknesses. The 2D KL-Si features electronic band gaps ranging from 2.82 to 1.36 eV as a function of increasing the layer thickness and hole/electron mobility as large as about 103 cm2·V–1·s–1. By applying the KL-Si to nanoscale FETs, we obtain giant negative differential resistances with peak-valley ratios over 107 and excellent switching performance fulfilling the requirements of the International Technology Roadmap for Semiconductors. Our study demonstrates the importance of kagome topology in the design of 2D Si crystals with excellent semiconducting properties as well as their promising application in nanoelectronic devices.

The Integration of Field Effect Transistors to Microfluidic Devices

Devices that integrate field effect transistors into microfluidic channels are becoming increasingly promising in the medical, environmental, and food realms, among other applications. The uniqueness of this type of sensor lies in its ability to reduce the background signals existing in the measurements, which interfere in obtaining good limits of detection for the target analyte. This and other advantages intensify the development of selective new sensors and biosensors with coupling configuration. This review work focused on the main advances in the fabrication and application of field effect transistors integrated into microfluidic devices as a way of identifying the potentialities that exist in these systems when used in chemical and biochemical analyses. The emergence of research on integrated sensors is not a recent study, although more recently the progress of these devices is more accentuated. Among the studies that used integrated sensors with electrical and microfluidic parts, those that investigated protein binding interactions seem to be the ones that expanded the most due, among other things, to the possibility of obtaining several physicochemical parameters involved in protein–protein interactions. Studies in this area have a great possibility of advancing innovations in sensors with electrical and microfluidic interfaces in new designs and applications.

Electronic Structures and Charge Mobilities of Several Regioisomeric B2N2-Substituted Perylenediimides.

Tunable and rich electronic properties of perylenediimide (PDI), an n-type semiconductor together with its synthetic ease and processibility, make it suitable for various optoelectronic and field-effect transistor applications. The electronic structures, spectroscopic properties, and charge mobilities for a few isoelectronic BN-substituted PDIs (B2N2-PDIs) with varied BN-patterning are studied using density functional theory (DFT) and time-dependent DFT employing optimally tuned range-separated hybrid. Two substitutional doping patterns, namely, BNNB and NBBN with zero dipole and also BNBN, the one with a finite dipole, are considered to explore the changes in the PDI properties due to different B2N2-substitutions. All three B2N2-PDIs are found to be dynamically stable and lie within a small energy window of ca. ∼1.7 kcal mol-1. An increased electronic gap due to charge localization produces a similar but slightly blue-shifted low-lying optical peak compared to the pristine PDI, in good agreement with the experimental observations. Additionally, differently considered BN patterns result in only slightly varied charge mobilities due to mainly differences in electronic couplings with larger electron mobilities found for the experimentally synthesized BNNB-PDI crystal. On the other hand, small reorganization energy and relatively large coupling for the hole transport produce greater hole mobilities for the NBBN-PDI. Varied nuclear reorganization and electronic coupling are understood by analyzing Huang-Rhys factors associated with normal modes and frontier molecular orbitals, respectively. These results serve as complementary to understanding the recently reported experimental findings and also provide new insights into the impact of different BN patterns on modulating the PDI electronic and charge-transport properties.

N-Type Doping of Naphthalenediimide-Based Random Donor–Acceptor Copolymers to Enhance Transistor Performance and Structural Crystallinity

An integrated strategy of molecular design and conjugated polymer doping is proposed to improve the electronic characteristics for organic field effect transistor (OFET) applications. Here, a series of soluble naphthalene diimide (NDI)-based random donor-acceptor copolymers with selenophene π-conjugated linkers and four acceptors with different electron-withdrawing strengths (named as rNDI-N/S/NN/SS) are synthesized, characterized, and used for OFETs. N-type doping of NDI-based random copolymers using (12a,18a)-5,6,12,12a,13,18,18a,19-octahydro-5,6-dimethyl-13,18[1',2']-benzenobisbenzimidazo[1,2-b:2',1'-d]benzo[i][2.5]benzodiazocine potassium triflate adduct (DMBI-BDZC) is successfully demonstrated. The undoped rNDI-N, rNDI-NN, and rNDI-SS samples exhibit ambipolar charge transport, while rNDI-S presents only a unipolar n-type characteristic. Doping with DMBI-BDZC significantly modulates the performance of rNDI-N/S OFETs, with a 3- to 6-fold increase in electron mobility (μe) for 1 wt % doped device due to simultaneous trap mitigation, lower contact resistance (RC), and activation energy (EA), and enhanced crystallinity and edge-on orientation for charge transport. However, the doping of intrinsic pro-quinoidal rNDI-NN/SS films exhibits unchanged or even reduced device performance. These findings allow us to manipulate the energy levels by developing conjugated copolymers based on various acceptors and quinoids and to optimize the dopant-polymer semiconductor interactions and their impacts on the film morphology and molecular orientation for enhanced charge transport.

Fluoro substitution effect on 2,1,3-benzothiadiazole-based hybridized local and charge transfer state fluorophores for high-performance organic light-emitting diodes

Fluoro substitution of organic semiconductors is an effective way to improve some related performance of the materials, such as the carrier mobility in organic photovoltaics (OPVs) and organic field-effect transistors (OFETs) applications. However, the influence of fluoro substitution for fluorophores in organic light-emitting diodes (OLEDs) applications is rarely reported. Here, with fluorinated electron-deficient 2,1,3-benzothiadiazole (BT) unit as the acceptor and triphenylamine (TPA) as the donor, we construct two new D-A-type fluorophores DTPA-fBT and DTPA-ffBT. Theoretical calculations and experimental results reveal that the lowest excited states (S1) of the materials are characterized by hybridized local and charge-transfer (HLCT) properties, in which the fluorine substitution will increase the proportion of the charge-transfer (CT) component. Due to the introduction of fluoro substitution, multiple fluorine hydrogen bonds are formed, which endow the molecules with more rigid conformation, leading to lower non-radiative rates and higher photoluminescence quantum yield (PLQY) in solution and doped film, as well as improved thermal stability in the solid state. As a result, the two fluorinated DTPA-ffBT demonstrate significantly improved performance in OLEDs with a maximum external quantum efficiency (EQE) of 7.25% (5.90% for fluorine-free counterpart) and very low-efficiency roll-off (roll-off <7% at 10,000 cd m−2).