A Green High-k Dielectric from Modified Carboxymethyl Cellulose-Based with Dextrin.

Many crucial components inside electronic devices are made from non-renewable, non-biodegradable, and potentially toxic materials, leading to environmental damage. Finding alternative green dielectric materials is mandatory to align with global sustainable goals. Carboxymethyl cellulose (CMC) is a bio-polymer derived from cellulose and has outstanding properties. Herein, citric acid, dextrin, and CMC based hydrogels are prepared, which are biocompatible and biodegradable and exhibit rubber-like mechanical properties, with Young modulus values of 0.89 MPa. Hence, thin film CMC-based hydrogel is explored as a suitable green high-k dielectric candidate for operation at low voltages, demonstrating a high dielectric constant of up to 78. These fabricated transistors reveal stable high capacitance (2090 nF cm-2) for ≈±3 V operation. Using a polyelectrolyte-type approach and poly-(2-vinyl anthracene) (PVAn) surface modification, this study demonstrates a thin dielectric layer (d ≈30 nm) with a small voltage threshold (Vth ≈-0.8 V), moderate transconductance (gm ≈65 nS), and high ON-OFF ratio (≈105). Furthermore, the dielectric layer exhibits stable performance under bias stress of ± 3.5 V and 100 cycles of switching tests. The modified CMC-based hydrogel demonstrates desirable performance as a green dielectric for low-voltage operation, further highlighting its biocompatibility.

Controlled Growth of Highly Oriented Perovskite Crystals in Polymer Solutions via Selective Solvent Vapor Diffusion.

Organic-inorganic hybrid perovskites have garnered significant attention in optoelectronics owing to their outstanding tunable optical characteristics. Controlled growth of perovskite nanocrystals from solutions is key for controlling the emission intensity and photoluminescence lifetime of perovskites. In particular, most studies have focused on controlling the crystallization of perovskite through chemical treatment using chelating ligands or physical treatment via antisolvent diffusion, and there exists a trade-off between the photoluminescence intensity and lifetime of perovskites. Herein, a selective solvent vapor-assisted crystallization with the aid of a functional polymer, which nanoscale perovskite crystals are grown andante from precursor solution, is presented for tuning the crystallization and optical properties of a common halide perovskite, methylammonium lead bromide (MAPbBr3 ). The proposed method here produces perovskite nanocrystals in the range of 200-300 nm. The spin-coated thin film formed from the perovskite solution exhibits strong green photoluminescence with a long lifetime. The effects of the functional group and polymer dosage on the crystallization of MAPbBr3 are systematically investigated, and the crystallization mechanism is explained based on a modified LaMer model. This study provides an advanced solution process for precisely controlling perovskite crystallization to enhance their optical properties for next-generation optoelectronic devices.

Room-Temperature Fabrication of p-Type SnO Semiconductors Using Ion-Beam-Assisted Deposition.

Over the past decade, SnO has been considered a promising p-type oxide semiconductor. However, achieving high mobility in the fabrication of p-type SnO films is still highly dependent on the post-annealing procedure, which is often used to make SnO, due to its metastable nature, readily convertible to SnO2 and/or intermediate phases. This paper demonstrates a fully room-temperature fabrication of p-type SnOx thin films using ion-beam-assisted deposition. This technique offers independent control between ion density, via the ion-gun anode current and oxygen flow rate, and ion energy, via the ion-gun anode voltage, thus being able to optimize the optical band gap and the hole mobility of the SnO films to reach 2.70 eV and 7.89 cm2 V-1 s-1, respectively, without the need for annealing. Remarkably, this is the highest mobility reported for p-type SnO films whose fabrication was carried out entirely at room temperature. Using first-principles calculations, we rationalize that the high mobility is associated with the fine-tuning of the Sn-rich-related defects and lattice densification, obtained by controlling the density and energy of the oxygen ions, both of which optimize the spatial overlap of the valence bands to form a continuous conduction path for the holes. Moreover, due to the absence of the annealing process, the Raman spectra reveal no significant signatures of microcrystal formation in the films. This behavior contrasts with the case involving the air-annealing procedure, where a complex interaction occurs between the formation of SnO microcrystals and the formation of SnOx intermediate phases. This interplay results in variations in grain texture within the film, leading to a lower optimum Hall mobility of only 5.17 cm2 V-1 s-1. Finally, we demonstrate the rectification characteristics of all-fabricated-at-room-temperature SnOx-based p-n devices to confirm the viability of the p-type SnOx films.

Unveiling the Photoinduced Recovery Mystery in Conjugated Polymer-Based Transistor Memory.

A straightforward mechanism for the photorecovery behavior of photoresponsive nonvolatile organic field-effect transistor (OFET) memories is proposed by employing a commercially available conjugated polymer, the poly(9,9-dioctylfluorene) (PFO), the conjugated monomer fluorene (FO), and the nonconjugated poly(vinyl alcohol) (PVA), as charge storage layers beneath the semiconducting pentacene layer. As photoexcitons are generated upon light exposure, the respective charges recombine with the trapped charges in electrets and neutralize the memory device. However, whether the excitons are generated in the semiconducting layer or the electret part, the origin that mainly governs the photorecovery behavior remains unclear. In this study, we show that when PVA, a nonphotoactive electret, replaces PFO the photorecovery behavior is totally absent, and it confirms the photorecovery behavior dominated by the excitons in situ generated in a charged electret. Moreover, PFO as a photoactive electret, exhibiting an excellent hole-trapping ability over 24 h in the dark and high Ion/Ioff current ratio of 108, has successfully demonstrated rapid photoinduced recovery under UV light. The devices also display a reliable switching ability between electrical charge trapping and optical recovery cycles for optical-recording application. This report presents a clear understanding behind photorecovery phenomena that demonstrates useful guidance to boost the development of photoactive OFET memories based on conjugated polymer electrets.

Tailoring Photophysical Properties of Diketopyrrolopyrrole Small Molecules with Electron-Withdrawing Moieties for Efficient Solar Steam Generation.

The development of photothermal materials (PTMs) for solar steam generation (SSG) has gained tremendous attention in response to the global clean water scarcity issue. However, the investigation in employing organic small-molecule PTMs for SSG applications is rarely found due to their narrow optical absorption range to harvest solar energy and insufficient photostability for long-term use. Herein, we employ a diketopyrrolopyrrole (DPP) core unit together with electron-withdrawing (EW) endcaps and siloxane side chains to introduce stronger intramolecular charge transfer (ICT) characteristics as well as the hydrophobic character. The enhanced ICT characteristics of DPP derivatives render a broad optical absorption range, less emission, and a high nonradiative decay rate for efficient solar energy harvesting and photothermal effects. Meanwhile, the hydrophobic nature of these DPP derivatives allows the facile fabrication of novel Janus photothermal membranes for effective water vaporization and solar-to-vapor conversion efficiency. By embedding DPP derivatives to the SSG device, we showed that the solar-to-vapor efficiency can reach up to 71.8% under relatively low visible light power (∼700 W m-2), which is, on average, 2.66 times higher than that of bulk water of similar dimension. Moreover, this report demonstrates the great potential of conjugated small molecules for photothermal applications, owing to their versatility and flexibility in structural engineering and its diminishing radiative decay properties. This may inspire more innovation and advancement in SSG applications.

Influence of Molecular Symmetry and Terminal Substituents on the Morphology and OFET Characteristics of S,N-Heteropentacenes.

Many heteroacenes have been extensively studied to improve device performances; however, the morphological effects stemmed from the chemical modification on a multiscale remain less explored. In this research, five axisymmetric S,N-heteropentacenes (DTPT, DTPT-Ph, DTPT-CN, DTPT-PYCN, and DTPT-BTCN) are studied to reveal the influences of molecular symmetry and end-capping substituents on the structure-property relationship, the thermal stability, crystallization behavior, film morphology, and OFET performance. Phase behavior was probed by differential scanning calorimetry (DSC), while the quality of the crystal array and structural details was investigated by optical microscopy (OM) and grazing-incidence wide-angle X-ray scattering (GIWAXS). The analytic results reveal that (1) the parent axisymmetric S,N-heteropentacene, DTPT, is hard to crystallize, which hinders the preparation of high-quality crystal arrays for the OFET application. (2) The incorporation of π-conjugated electron-withdrawing (π-EW) endcaps that provide extended conjugation length and enhanced molecular polarity is required to form oriented crystal arrays to deliver reasonable OFET characteristics. (3) The π-EW endcaps with conformational freedom, such as -BTCN, due to the asymmetric feature of benzothiadiazole (BT), can hinder bulk phase crystallization and cause conformational disorder in the crystal array. Hence, the tradeoff of introducing the end-substituents to reinforce the poor crystalline nature of S,N-heteroacenes should be carefully considered.

n-Type Thin-Film Transistors Based on Diketopyrrolopyrrole Derivatives: Role of Siloxane Side Chains and Electron-Withdrawing Substituents.

The physical properties, packing, morphology, and semiconducting performance of a planar π-conjugated system can be effectively modified by introducing side chains and substituent groups, both of which can be complementary to the π framework in changing the intermolecular association, frontier molecular orbital energy, optical band gap, and others. We herein show that installation of end-capped electron-withdrawing groups (EWGs), such as dicyanovinyl (-DCV), 3-ethylrhodanine (-RD), and 2-(3-oxo-indan-1-ylidene)-malononitrile (-INCN), together with siloxane side chains to the backbones of dithienyldiketopyrrolopyrrole (DPPT), such as DPPT-Si-DCV, DPPT-Si-RD, and DPPT-Si-INCN, can greatly improve its solubility, air stability, and film morphology to serve as an n-channel in thin-film transistor fabrication. The EWGs attached to the DPPT core narrowed the optical band gap (Egopt) and changed the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies (EHOMO and ELUMO), making them suitable for n-channel field-effect transistor (FET) applications. The benefits of introducing siloxane side chains to the DPPT core include enhanced solubility, low crystallization barrier, enantiotropic phase behavior, and much improved FET performance. The DPPT-Si-INCN film displayed low-lying HOMO (-5.82 eV) and LUMO (-4.60 eV) energy levels and an optical band gap as low as 1.22 eV, all of which suggest that this derivative can be quite resistant toward aerial oxidation. Thin films of these derivatives were prepared by the solution-shear method. A comparison of the solution-sheared films indicated that the molecular packing motif of DPPT-Si-INCN film was somehow different from that of DPPT-Si-DCV and DPPT-Si-RD, in which the π-π stacking tended to align orthogonally to the shearing direction. This specific π-π stacking alignment could have an impact on the electron mobility (µe) values in transistors based on the solution-sheared films.

Benzophenanthrothiophenes: Syntheses, Crystal Structures, and Properties.

A new class of polycyclic heteroarenes based on benzo[3,4]phenanthro[1,2-b]benzo[3,4]phenanthro[2,1-d]thiophene (BPBPT) was prepared from polyaryl thiophenes via regioselective Scholl reactions. The molecular frameworks of these compounds exhibited twisted bridges and near-cofacial packing motifs with oppositely or parallel π-stacked structures depending on the substituents on the periphery. Theoretical calculation of electronic coupling and charge mobility was carried out on the basis of the single-crystal structures. Single crystals of selected benzophenanthrothiophenes were used in p-channel field-effect transistor device fabrication, from which the highest mobility was measured as 2.03 cm2 V-1 s-1 from Flu-BPBPT.