50-nm Self-Aligned and “Standard” T-gate InP pHEMT Comparison: The Influence of Parasitics on Performance at the 50-nm Node

Continued research into the development of III-V high-electron mobility transistors (HEMTs), specifically the minimization of the device gate length, has yielded the fastest performance reported for any three terminal devices to date. In addition, more recent research has begun to focus on reducing the parasitic device elements such as access resistance and gate fringing capacitance, which become crucial for short gate length device performance maximization. Adopting a self-aligned T-gate architecture is one method used to reduce parasitic device access resistance, but at the cost of increasing parasitic gate fringing capacitances. As the device gate length is then reduced, the benefits of the self-aligned gate process come into question, as at these ultrashort-gate dimensions, the magnitude of the static fringing capacitances will have a greater impact on performance. To better understand the influence of these issues on the dc and RF performance of short gate length InP pHEMTs, the authors present a comparison between In_0.7Ga_0.3As channel 50-nm self-aligned and "standard" T-gate devices. Figures of merit for these devices include transconductance greater than 1.9 S/mm, drive current in the range 1.4 A/mm, and fT up to 490 GHz. Simulation of the parasitic capacitances associated with the self-aligned gate structure then leads a discussion concerning the realistic benefits of incorporating the self-aligned gate process into a sub-50-nm HEMT system     

High-Gain Chemically Gated Organic Electrochemical Transistor

Organic electrochemical transistors (OECTs) have exhibited promising performance as transducers and amplifiers of low potentials due to their exceptional transconductance, enabled by the volumetric charging of organic mixed ionic/electronic conductors (OMIECs) employed as the channel material. OECT performance in aqueous electrolytes as well as the OMIECs’ redox activity has spurred a myriad of studies employing OECTs as chemical transducers. However, the OECT's large (potentiometrically derived) transconductance is not fully leveraged in common approaches that directly conduct chemical reactions amperometrically within the OECT electrolyte with direct charge transfer between the analyte and the OMIEC, which results in sub-unity transduction of gate to drain current. Hence, amperometric OECTs do not truly display current gains in the traditional sense, falling short of the expected transistor performance. This study demonstrates an alternative device architecture that separates chemical transduction and amplification processes on two different electrochemical cells. This approach fully utilizes the OECT's large transconductance to achieve current gains of 10³ and current modulations of four orders of magnitude. This transduction mechanism represents a general approach enabling high-gain chemical OECT transducers.     

Modular and Versatile Spatial Functionalization of Tissue Engineering Scaffolds through Fiber‐Initiated Controlled Radical Polymerization

Native tissues are typically heterogeneous and hierarchically organized, and generating scaffolds that can mimic these properties is critical for tissue engineering applications. By uniquely combining controlled radical polymerization (CRP), end‐functionalization of polymers, and advanced electrospinning techniques, a modular and versatile approach is introduced to generate scaffolds with spatially organized functionality. Poly‐ε‐caprolactone is end functionalized with either a polymerization‐initiating group or a cell‐binding peptide motif cyclic Arg‐Gly‐Asp‐Ser (cRGDS), and are each sequentially electrospun to produce zonally discrete bilayers within a continuous fiber scaffold. The polymerization‐initiating group is then used to graft an antifouling polymer bottlebrush based on poly(ethylene glycol) from the fiber surface using CRP exclusively within one bilayer of the scaffold. The ability to include additional multifunctionality during CRP is showcased by integrating a biotinylated monomer unit into the polymerization step allowing postmodification of the scaffold with streptavidin‐coupled moieties. These combined processing techniques result in an effective bilayered and dual‐functionality scaffold with a cell‐adhesive surface and an opposing antifouling non‐cell‐adhesive surface in zonally specific regions across the thickness of the scaffold, demonstrated through fluorescent labelling and cell adhesion studies. This modular and versatile approach combines strategies to produce scaffolds with tailorable properties for many applications in tissue engineering and regenerative medicine.     

Linking Glass-Transition Behavior to Photophysical and Charge Transport Properties of High-Mobility Conjugated Polymers

The measurement of the mechanical properties of conjugated polymers can reveal highly relevant information linking optoelectronic properties to underlying microstructures and the knowledge of the glass transition temperature (T_g) is paramount for informing the choice of processing conditions and for interpreting the thermal stability of devices. In this work, we use dynamical mechanical analysis to determine the T_g of a range of state-of-the-art conjugated polymers with different degrees of crystallinity that are widely studied for applications in organic field-effect transistors. We compare our measured values for T_g to the theoretical value predicted by a recent work based on the concept of effective mobility ζ. The comparison shows that for conjugated polymers with a modest length of the monomer units, the T_g values agree well with theoretically predictions. However, for the near-amorphous, indacenodithiophene–benzothiadiazole family of polymers with more extended backbone units, values for T_g appear to be significantly higher, predicted by theory. However, values for T_g are correlated with the sub-bandgap optical absorption suggesting the possible role of the interchain short contacts within materials’ amorphous domains.     

The Influence of Film Morphology in High‐Mobility Small‐Molecule:Polymer Blend Organic Transistors

Organic field‐effect transistors (OFETs) based upon blends of small molecular semiconductors and polymers show promise for high performance organic electronics applications. Here the charge transport characteristics of high mobility p‐channel organic transistors based on 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl) anthradithiophene:poly(triarylamine) blend films are investigated. By simple alteration of the film processing conditions two distinct film microstructures can be obtained: one characterized by small spherulitic grains (SG) and one by large grains (LG). Charge transport measurements reveal thermally activated hole transport in both SG and LG film microstructures with two distinct temperature regimes. For temperatures >115 K, gate voltage dependent activation energies (E_A) in the range of 25–60 meV are derived. At temperatures <115 K, the activation energies are smaller and typically in the range 5–30 meV. For both film microstructures hole transport appears to be dominated by trapping at the grain boundaries. Estimates of the trap densities suggests that LG films with fewer grain boundaries are characterized by a reduced number of traps that are less energetically disordered but deeper in energy than for small SG films. The effects of source and drain electrode treatment with self‐assembled monolayers (SAMs) on current injection is also investigated. Fluorinated thiol SAMs were found to alter the work function of gold electrodes by up to ～1 eV leading to a lower contact resistance. However, charge transport analysis suggests that electrode work function is not the only parameter to consider for efficient charge injection.     

Anisotropy of Charge Transport in a Uniaxially Aligned and Chain‐Extended,High‐Mobility,Conjugated Polymer Semiconductor

Charge transport in the ribbon phase of poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT)—one of the most highly ordered, chain‐extended crystalline microstructures available in a conjugated polymer semiconductor—is studied. Ribbon‐phase PBTTT has previously been found not to exhibit high carrier mobilities, but it is shown here that field‐effect mobilities depend strongly on the device architecture and active interface. When devices are constructed such that the ribbon‐phase films are in contact with either a polymer gate dielectric or an SiO₂ gate dielectric modified by a hydrophobic, self‐assembled monolayer, high mobilities of up to 0.4 cm² V^?1 s^?1 can be achieved, which is comparable to those observed previously in terrace‐phase PBTTT. In uniaxially aligned, zone‐cast films of ribbon‐phase PBTTT the mobility anisotropy is measured for transport both parallel and perpendicular to the polymer chain direction. The mobility anisotropy is relatively small, with the mobility along the polymer chain direction being higher by a factor of 3–5, consistent with the grain size encountered in the two transport directions.     

Role of the Anion on the Transport and Structure of Organic Mixed Conductors

Organic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium‐ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte‐mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.     

The Effect of Alkyl Spacers on the Mixed Ionic-Electronic Conduction Properties of N-Type Polymers

Conjugated polymers with mixed ionic and electronic transport are essential for developing the complexity and function of electrochemical devices. Current n-type materials have a narrow scope and low performance compared with their p-type counterparts, requiring new molecular design strategies. This work presents two naphthalene diimide-bithiophene (NDI-T2) copolymers functionalized with hybrid alkyl-glycol side chains, where the naphthalene diimide unit is segregated from the ethylene glycol (EG) units within the side chain by an alkyl spacer. Introduction of hydrophobic propyl and hexyl spacers is investigated as a strategy to minimize detrimental swelling close to the conjugated backbone and balance the mixed conduction properties of n-type materials in aqueous electrolytes. It is found that both polymers functionalized with alkyl spacers outperform their analogue bearing EG-only side chains in organic electrochemical transistors (OECTs). The presence of the alkyl spacers also leads to remarkable stability in OECTs, with no decrease in the ON current after 2 h of operation. Through this versatile side chain modification, this work provides a greater understanding of the structure-property relationships required for n-type OECT materials operating in aqueous media.     

Bimolecular Crystals of Fullerenes in Conjugated Polymers and the Implications of Molecular Mixing for Solar Cells

The performance of polymer:fullerene bulk heterojunction solar cells is heavily influenced by the interpenetrating nanostructure formed by the two semiconductors because the size of the phases, the nature of the interface, and molecular packing affect exciton dissociation, recombination, and charge transport. Here, X‐ray diffraction is used to demonstrate the formation of stable, well‐ordered bimolecular crystals of fullerene intercalated between the side‐chains of the semiconducting polymer poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene. It is shown that fullerene intercalation is general and is likely to occur in blends with both amorphous and semicrystalline polymers when there is enough free volume between the side‐chains to accommodate the fullerene molecule. These findings offer explanations for why luminescence is completely quenched in crystals much larger than exciton diffusion lengths, how the hole mobility of poly(2‐methoxy‐5‐(3′,7′‐dimethyloxy)‐p‐phylene vinylene) increases by over 2 orders of magnitude when blended with fullerene derivatives, and why large‐scale phase separation occurs in some polymer:fullerene blend ratios while thermodynamically stable mixing on the molecular scale occurs for others. Furthermore, it is shown that intercalation of fullerenes between side chains mostly determines the optimum polymer:fullerene blending ratios. These discoveries suggest a method of intentionally designing bimolecular crystals and tuning their properties to create novel materials for photovoltaic and other applications.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.