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The journal of physical chemistry / C 127(2), 1156 - 1166 (2023). doi:10.1021/acs.jpcc.2c06161, The semiconducting bithiophene systems are largely unexplored structurally at high-pressures. Here, we characterize the high-pressure structure and phase behavior of 5,5′-bis(naphth-2-yl)-2,2′-bithiophene (NaT2) by single crystal X-ray diffraction, photoluminescence and Raman compression measurements in the diamond anvil cell to 7.6 GPa. Experimental results are supported by empirical interaction energy calculations. NaT2 maintains its ambient pressure structure (P2$_1$/c) on compression but undergoes a subtle second-order phase transition at ca. 3.5 GPa. The newly formed phase at 4.0 GPa is characterized by the formation of a new S···H interaction between thiophene moieties in adjacent molecules, as well as by the emergence of a more favorable compression pathway in its long-chain direction. NaT2 also undergoes a band gap closure manifested as a distinct yellow to red color change on compression that is fully reversible on decompression., Published by Soc., Washington, DC

Replacing S with Se in fluorinated isoindigo (IID) copolymers enhances charge transport properties in field-effect transistors (FET). Nonlinear optical imaging from IID FETs helps visualize transport.

The solution processability of organic semiconductors and conjugated polymers along with the advent of nanomaterials as conducting inks have revolutionized next-generation flexible consumer electronics. Another equally important class of nanomaterials, self-assembled peptides, heralded as next-generation materials for bioelectronics, have a lot of potential in printed technology. In this minireview, we address the self-assembly process in dipeptides, their application in electronics, and recent progress in three-dimensional printing. The prospect of a generalizable path for nanopatterning self-assembled peptides using ice lithography and its challenges are further discussed.

While the layered hybrid Ruddlesden-Popper (RP) halide perovskites have already established themselves as the frontrunners among the candidates in optoelectronics, their all-inorganic counterparts remain least explored in the RP-type perovskite family. Herein, we study and compare the optoelectronic properties of all-inorganic CsPbBr3 perovskite nanocrystals (PNCs) with and without RP planar faults. We find that the RP-CsPbBr3 PNCs possess both higher exciton binding energy and longer exciton lifetimes. The former is ascribed to a quantum confinement effect in the PNCs induced by the RP faults. The latter is attributed to a spatial electron-hole separation across the RP faults. A striking difference is found in the up-conversion photoluminescence response in the two types of CsPbBr3 PNCs. For the first time, all-inorganic RP-CsPbBr3 PNCs are tested in light-emitting devices and shown to significantly outperform the non-RP CsPbBr3 PNCs.

Chemical vapor deposition (CVD), a low-cost and a scalable deposition technique, allows the growth of methylammonium lead iodide (MAPbI3) films without the use of solvents, substantially increasing air stability while also inducing the stable cubic phase at room temperature and at pressures as low as 0.25 GPa. MAPbI3 thin films were grown by a facile two-step low-pressure vapor deposition process in a single reactor. This method results in films, which are usually in the tetragonal phase (space group: I4/mcm) and occasionally in the cubic phase under ambient conditions. High-pressure synchrotron-based X-ray diffraction studies from CVD-grown MAPbI3 crystallites show that the sample remains in the cubic phase (space group: Im $$\bar{3}$$ ) between 0.25 and 3.0 GPa. Temperature-dependent transport measurements show sharp anomalies, correlating with the structural changes. The transport measurements from the CVD-grown cubic MAPI3 film is further compared with a film in the tetragonal phase.

The use of high κ dielectrics lowers the operating voltage in organic field-effect transistors (FETs). Polymer ferroelectrics open the path not just for high κ values but allow processing of the dielectric films via electrical poling. Poled ferroelectric dielectrics in p-type organic FETs was seen to improve carrier mobility and reduce leakage current when compared to unpoled devices using the same dielectric. For n-type FETs, solution-processed ZnO films provide a viable low-cost option. UV–ozone-treated ZnO films was seen to improve the FET performance due to the filling of oxygen vacancies. P-type FETs were fabricated using the ferroelectric polymer poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) as the dielectric along with a donor–acceptor polymer based on diketopyrrolopyrrole (DPP-DTT) as the semiconductor layer. The DPP-DTT FETs yield carrier mobilities upwards of 0.4 cm2/Vs and high on/off ratios when the PVDF-TrFE layer is electrically poled. For n-type FETs, UV–ozone-treated sol–gel ZnO films on SiO2 yield carrier mobilities of 10−2 cm2/Vs. DPP-DTT-based p- and ZnO-based n-type FETs were used in a complementary voltage inverter circuit, showing promising characteristic gain. A basic inverter model was used to simulate the inverter characteristics, using parameters from the individual FET characteristics.

Mixed halide perovskites with chlorine (Cl) content have received significant interest due to better charge transport properties and longer diffusion length compared to pure iodine-based perovskites. The superior properties of Cl-doped perovskites improve solar cell device performance, although the quantification of Cl composition in the perovskite films remain difficult to achieve. Hence, it is difficult to correlate the Cl-quantity with the improved device performance. In this work, we deposited Cl-doped perovskite films through a facile three- and two-step sequential chemical vapor deposition (CVD) where lead halide films were deposited in the first steps of the process and subsequently converted to perovskites. No Cl substitution by iodine was observed during a sequential deposition of lead chloride and lead iodide films which reacted to form a lead chloride iodide phase (PbICl). The substitution of Cl by iodine ions only occurred during the conversion to perovskite phase. Large perovskite grains (greater than 2 µm) were realized when converting a PbI2 film to perovskite compared to chlorine containing lead halide films, contradicting literature. However, Cl doped perovskite solar cells showed improved device efficiencies as high as 10.87% compared to an un-doped perovskite solar cell (8.76%).

Lead halide perovskites have a rich landscape of structural and optical properties, which can be explored and possibly controlled by applying high pressure. Despite several reports on high-pressure...

Organic–inorganic interfaces in photodiodes have recently gathered significant interest due to the realization of intrinsic p–n junctions and unique physical properties. Nanopatterned sol–gel ZnO f...

The detection of pathogens in low concentrations is a major challenge. Electrochemical biosensor provide a viable solution because they are low cost, fast, and miniaturized. However, due to the complexity of biological samples, there is a need to create devices that enable signal amplification, which are more sensitive, specific, and biocompatible. Organic electrochemical transistors (OECTs) are an important technological alternative to be applied in diagnosis area. Transistors measure the intensity of the electrical current that flows between the source and drain electrodes that is proportional to an electric field applied to a third electrode, called gate. OECTs use small organic molecules and conjugated macromolecules as semiconductors, in addition to an electrolytic layer, which allows biosensing applications. They are promising for the analysis of electroactive biological species, which can be directly reduced or oxidized at the electrode interface. Further, redox inactive biological species may be analyzed through molecular biorecognition. Due to the unique characteristics of signal amplification, OECTs are an option for the development of a wide range of customized point-of-care test tools for clinical diagnosis and therapeutic applications.

The charge carrier mobility in organic field-effect transistors (FETs) may be enhanced by a few orders of magnitude by an appropriate choice of the dielectric layer. Polymer ferroelectric dielectrics with their high dielectric constants are attractive for low-operating voltage FETs. However, due to the dynamic coupling of the charge carriers to the electronic polarization at the semiconductor-dielectric interface, polymer ferroelectric based organic FETs may result in low carrier mobilities. Selective electrical poling of the ferroelectric dielectric, poly(vinylidene fluoride trifluorethylene) (PVDF-TrFE), is seen to greatly improve the performance of small molecule and donor-acceptor copolymer based FETs [1]. A combination of vertical and lateral poling of the PVDF-TrFE layer, which reduces the gate leakage current as well as mitigates polarization fluctuation driven transport, yields carrier mobilities upwards of 1 cm2/Vs in TIPS-pentacene and 0.5 cm2/Vs in diketopyrrolopyrrole based FETs under ambient conditions [2]. Other strategies for improving the performance of FETs involve dissolving the ferroelectric polymer in high dipole moment solvents and adding thin polymer buffer layers. The incorporation of magnetic nanoparticles in non-ferroelectric dielectrics is yet another approach for enhancing the dielectric constant. Ferrite nanoparticles with biomimetic peptide nanostructures as gate dielectrics have ramifications in low-operating voltage organic FETs [3]. This work was supported by National Science Foundation under Grant No. ECCS-1707588 [1] Laudari et al. Adv. Mater. Interfaces 6, 1801787 (2019). [2] Laudari et al. ACS Appl. Mater. Interfaces 12, 26757 (2020). [3] Khanra et al. ACS Appl. Nano Mater 1, 1175 (2018).

Lead halide perovskites provide a test bed for exploring nonlinear optical properties. Although the underlying centrosymmetric crystal structure of 3D lead halide perovskites precludes the phenomenon of second harmonic generation, the third and higher-order harmonic generation are allowed. In this work, we probe the third harmonic generation (THG) from CsPbBr3 nanocrystals (NCs) and compare it to the THG from CsPbBr3 NCs with Ruddlesden-Popper planar faults (RP-CsPbBr3), formed via postsynthetic fusion-growth. The THG from CsPbBr3 NCs is negligible compared with that of RP-CsPbBr3 NCs within a wide range of femtosecond excitation wavelengths. We further compare the THG from a thin film of RP-CsPbBr3 with that of a single crystal of methylammonium lead bromide (MAPbBr3). The THG efficiency of RP-CsPbBr3 is found to be three times greater than that of MAPbBr3. An effective third-order susceptibility of the order of 10-18 m2 V-2 is obtained for a RP-CsPbBr3 film, opening up the prospect of inorganic halide perovskite NCs with planar defects for a range of nonlinear optical applications.

An alternative label-free electrochemical immunosensor for the rapid detection of Leishmania braziliensis was developed by immobilizing a peptide-based probe of the promastigote surface antigen (PS...

Hybrid organic-inorganic semiconducting interfaces have attracted attention in photodiodes and field-effect transistors (FETs) due to the realization of intrinsic p-n junctions and their mechanical flexibility. With the difficulty of developing high-mobility n-type organic semiconductors due to the necessity of low LUMO levels and ambient environment stability, solution processable inorganic materials are an excellent alternative. ZnO is an intrinsic n-type semiconductor which is non-toxic and sol-gel processable, creating avenues for film patterning and fully solution processed devices. We report the improvement of electron mobilities in ZnO FETs through simple UV-Ozone processing which reduces lattice defects within the film and at the SiO2/ZnO interface. Treated ZnO films yield electron mobilities close to 10-2 cm2/Vs and on/off current ratios of 104 while non-treated films have mobilities on the order of 10-5 cm2/Vs and an order of magnitude lower on/off current ratios. Treated films also yield improved photoresponsivity and detectivity in hybrid ZnO-organic photodetectors. Copyright © Materials Research Society 2019.

Organic-inorganic hybrid metal-halide perovskite (OIHP) materials provide a tunable platform for engineering their optoelectronic properties. Although several high-pressure studies have been conducted from the OIHP family of single crystals and films, the exact nature of the dynamic coupling of the $\mathrm{C}{\mathrm{H}}_{3}\mathrm{N}{\mathrm{H}}_{3}$ (MA) cation with the octahedral lattice framework and the mechanisms responsible for the structural phase transformation under pressure are not well captured. By combined photoluminescence (PL), synchrotron-based x-ray diffraction, and Raman-scattering studies as a function of pressure from methylammonium lead bromide ($\mathrm{M}\mathrm{A}\mathrm{Pb}{\mathrm{Br}}_{3}$), we shed light on an isostructural phase transition due to the coupling of the MA cation and the $\mathrm{Pb}{\mathrm{Br}}_{6}$ lattice through hydrogen bonding. The sharp discontinuities at $\ensuremath{\sim}$ 1 GPa and $\ensuremath{\sim}$ 3 GPa in the PL peak positions correlate with the structural changes observed in high-pressure XRD and Raman-scattering studies. The electronic band edge as a function of pressure is calculated within density-functional theory. The PL peak position, intensity and width of the excitonic peak show significant changes at 2 GPa, which corroborate the changes observed in high-pressure Raman-scattering studies. The frequencies of the lattice modes and the C--H/N--H bending and stretching modes of the MA cation show anomalous changes and other nuances at 2 GPa. The suppression of rotational and orientational disorder of the organic moiety is initiated at 2 GPa and the ordering is completed by 3.0 GPa, leading to an order-disorder type cubic II ($Im\overline{3}$) to orthorhombic ($Pnma$) phase transition. Along with the revelation of an isostructural transformation at 2 GPa, this paper highlights the impact of molecular vibrations on the electronic properties of $\mathrm{M}\mathrm{A}\mathrm{Pb}{\mathrm{Br}}_{3}$ under pressure.

The strong spin–orbit coupling (SOC) in lead halide perovskites, when inversion symmetry is lifted, has provided opportunities for investigating the Rashba effect in these systems. Moreover, the strong orbital moment, which, in turn, impacts the spin-pair in singlet and triplet electronic states, plays a significant role in enhancing the optoelectronic properties in the presence of external magnetic fields in lead halide perovskites. Here, we investigate the effect of weak magnetic fields (

Both the semiconductor-dielectric interface and the presence of polymorphs in the semiconducting layer of an organic field-effect transistor (FET) dictate charge transport. Grazing incidence X-ray diffraction (GIXRD) from a side-chain-substituted thiophene DPP monomer (Ph-TDPP-Ph) reveal the presence of two triclinic phases. The FET carrier mobilities change by orders of magnitude depending on the ratio of the two triclinic phases. We further demonstrate the prospect of enhancing device performance of a DPP copolymer-based FET by texture poling of a ferroelectric dielectric layer. Such devices in conjunction with n-type sol-gel processed ZnO FET are promising in voltage inverter circuits.

The use of polymer ferroelectric dielectrics in organic field-effect transistors (FETs) for nonvolatile memory application was demonstrated more than 15 years ago. The ferroelectric dielectric polyvinylidene fluoride (PVDF) and its copolymers are most widely used for such applications. In addition to memory applications, polymer ferroelectrics as a dielectric layer in organic FETs yield insights into interfacial transport properties. Advantages of polymer ferroelectric dielectrics are their high dielectric constant compared to other polymer dielectrics and their tunable dielectric constant with temperature. Further, the polarization strength may also be tuned by externally poling the ferroelectric dielectric layer. Thus, PVDF and its copolymers provide a unique testbed not just for investigating polarization induced transport in organic FETs, but also enhancing device performance. This article discusses recent developments of PVDF-based ferroelectric organic FETs and capacitors with a focus on tuning transport properties. It is shown that FET carrier mobilities exhibit a weak temperature dependence as long as the dielectric is in the ferroelectric phase, which is attributed to a polarization fluctuation driven process. The low carrier mobilities in PVDF-based FETs can be enhanced by tuning the poling condition of the dielectric. In particular, by using solution-processed small molecule semiconductors and other donor-acceptor copolymers, it is shown that selective poling of the PVDF-based dielectric layer dramatically improves FET properties. Finally, the prospects of further improvement in organic ferroelectric FETs and their challenges are provided.

Copolymers based on diketopyrrolopyrrole (DPP) cores have attracted a lot of attention because of their high p-type as well as n-type carrier mobilities in organic field-effect transistors (FETs) and high power conversion efficiencies in solar cell structures. We report the structural and charge transport properties of n-dialkyl side-chain-substituted thiophene DPP end-capped with a phenyl group (Ph-TDPP-Ph) monomer in FETs which were fabricated by vacuum deposition and solvent coating. Grazing-incidence X-ray diffraction (GIXRD) from bottom-gate, bottom-contact FET architectures was measured with and without biasing. Ph-TDPP-Ph reveals a polymorphic structure with π-conjugated stacking direction oriented in-plane. The unit cell comprises either one monomer with a = 20.89 Å, b = 13.02 Å, c = 5.85 Å, α = 101.4°, β = 90.6°, and γ = 94.7° for one phase (TR1) or two monomers with a = 24.92 Å, b = 25.59 Å, c = 5.42 Å, α = 80.3°, β = 83.5°, and γ = 111.8° for the second phase (TR2). The TR2 phase thus signals a shift from a coplanar to herringbone orientation of the molecules. The device performance is sensitive to the ratio of the two triclinic phases found in the film. Some of the best FET performances with p-type carrier mobilities of 0.1 cm2/V s and an on/off ratio of 106 are for films that comprise mainly the TR1 phase. GIXRD from in operando FETs demonstrates the crystalline stability of Ph-TDPP-Ph.

Here, we report the functionalization of diphenylalanine (FF)-based self-assembled nanotubes with cobalt ferrite (CFO) magnetic nanoparticles. Electron microscopy images show the CFO nanoparticles to be uniformly dispersed on the peptide nanotubes. We investigate the interaction between CFO nanoparticles and FF nanotubes by optical spectroscopy, X-ray photoelectron spectroscopy (XPS), and magnetization measurements. The changes in the XPS data from pristine FF nanotubes and CFO:FF nanotubes are indicative of charge transfer from CFO to FF nanotubes, changing the electronic states of the Fe2+ and Co2+ ions. The A1g Raman peak of CFO at 675 cm–1 hardens in CFO:FF nanotubes, signaling an enhancement of the stiffness constant of the iron–oxygen bond due to charge transfer. A comparison of the magnetic characterization from CFO nanoparticles and the CFO:FF nanocomposite shows a higher saturation magnetization from the nanocomposite, which is attributed to a change in the cationic distribution in CFO upon bindi...

A series of organometallic complexes and polymers has been synthesized with an objective of studying their fundamental photophysical properties together with their organic photovoltaic and organic field-effect transistor properties. The metal chromophores consist of a diketopyrrolopyrrole (DPP) core, end functionalized with cyclometalated platinum “auxochrome”. The photophysical properties of the metal complex and polymers are compared with the unmetalated chromophore DPP-C8-Th-Py. The polymers Poly-DPP-Th-Pt and Poly-DPP-Ph-Pt differ structurally in their cyclometallating ligands, where they consist of 2-thienylpyridine and 2-phenylpyridine, respectively. Efficient solar spectrum coverage was observed for all chromophores; specifically, the polymer Poly-DPP-Th-Pt has an onset of absorption at ∼900 nm with an optical band gap of 1.4 eV. The triplet excited state was detected for all chromophores and probed by both nanosecond and picosecond transient absorption spectroscopy. Both polymers were employed as ...

Hybrid organic-inorganic photodiode interfaces have gained significant interest due to their unique physical properties such as mechanical flexibility and high photosensitivity. Two diketopyrrolopyrrole (DPP)-based donor-acceptor copolymers with different backbone conformations are characterized in an inverted non-fullerene photodiode architecture using ZnO nano-patterned films as the electron transport layer. The DPP copolymer with a thienothiophene unit (PBDT-TIDPP) is more planar and rigid compared to the DPP system with a thiophene unit connecting the donor and acceptor moieties within the monomer (PBDT-TDPP). The hybrid interfaces were optimized by using poly(3-hexylthiophene) (P3HT) as the p-type layer for monitoring the critical thickness and morphology of the ZnO layer. The maximum photoresponsivity from a P3HT:ZnO photodiode was found to be 56 mA/W. The photoresponsivity of PBDT-TTDPP:ZnO photodiodes were found to be more than two orders of magnitude higher than PBDT-TDPP:ZnO photodiodes, which is attributed to an enhanced transport of carriers due to the planar backbone conformation of the PBDT-TTDPP copolymer. Capacitance-voltage measurements from hybrid Schottky barrier interfaces further shed light into the nature of photocarriers and device parameters. First-principles time-dependent density-functional theoretical calculations yield a higher absorptivity for the PBDT-TTDPP dimer compared to PBDT-TDPP. (C) 2017 Elsevier B.V. All rights reserved.

A comparative study of ferroelectric and non-ferroelectric-gated organic field-effect transistors (FETs) have been carried out by using a small molecule semiconductor 6,13 bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) to understand the fundamental aspects of carrier transport in FET architectures. Temperature-dependent current-voltage characteristics from non-ferroelectric dielectric-gated FETs show a clear activated transport, independent of the dielectric constant. While using the ferroelectric dielectric polymer poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE), where the dielectric constant may be tuned by changing the temperature, a negative temperature coefficient of the carrier mobility is observed beyond 200 K. The polarization fluctuation dominant transport inherent to a ferroelectric dielectric in conjunction with the discrete nature of traps in TIPS-pentacene results in an effective de-trapping of the shallow trap states into more mobile states.

Epitaxial graphene on SiC provides both an excellent source of high-quality graphene as well as an architecture to support its application. Although single-layer graphene on Si-face SiC has garnered extensive interest, many-layer graphene produced on C-face SiC could be significantly more robust for enabling applications. Little is known, however, about the structural properties related to the growth evolution at the buried interface for thick many-layer graphene. Using complementary X-ray scattering and neutron reflectivity as well as electron microscopy, we demonstrate that thick many-layer epitaxial graphene exhibits two vastly different length-scales of the buried interface roughness as a consequence of the Si sublimation that produces the graphene. Over long lateral length-scales the roughness is extremely large (hundreds of A) and it varies proportionally to the number of graphene layers. In contrast, over much shorter lateral length-scales we observe an atomically abrupt interface with SiC terraces. Graphene near the buried interface exhibits a slightly expanded interlayer spacing (∼1%) and fluctuations of this spacing, indicating a tendency for disorder near the growth front. Nevertheless, Dirac cones are observed from the graphene while its domain size routinely reaches micron length-scales, indicating the persistence of high-quality graphene beginning just a short distance away from the buried interface. Discovering and reconciling the different length-scales of roughness by reflectivity was complicated by strong diffuse scattering and we provide a detailed discussion of how these difficulties were resolved. The insight from this analysis will be useful for other highly rough interfaces among broad classes of thin-film materials.

Journal of polymer science / B 57(7), 392 - 396 (2019). doi:10.1002/polb.24793, We report on X-ray scattering measurements of heli-cal poly[9,9-bis(2-ethylhexyl)-fluorene-2,7-diyl] by mapping thesample with 10μm spatial resolution from 0.3 GPa to 36 GPa.We follow the strongest 00lreflection, which moves towardhigher scattering angles with pressure indicating planarizationof helical polyfluorene. Lateral inhomogeneity is increased for>10 GPa concomitant with the solidification of the pressure transmitting medium (a 4:1 mixture of methanol and ethanol) We also follow the 00l reflection with increasing temperature atthe constant pressure of 4.3 GPa in neon. We observe a sharpshift toward higher scattering angles indicative of a phase transi-tion at 167–176C., Published by Wiley, Bognor Regis [u.a.]

Peptide-based scaffolds are a frontier research area in materials science with widespread impact in biomedical engineering. In this paper, we describe a hybrid material formulated through the conjugation of electrospun polycaprolactone (PCL) fibers and micro/nanotubes of l,l-diphenylalanine (FF-MNTs). Morphology and crystallinity of the composite matrices are investigated using a wide range of analytical techniques including electron microscopy, thermal analyses, X-ray diffraction and micro-tomography. Peptide assemblies are found to produce deep modifications on the microstructure of PCL fibers, impacting average diameters, crystallinity degree and porous size in the polymer network. These changes are correlated with mechanical properties of the resulting scaffolds, whose strength is found to exhibit a brittle-to-ductile transition upon increasing the amount of FF-MNTs and lead to enhanced Young's moduli of polymer fibers. The PCL/FF-MNTs composites were tested for the drug delivery application of a lipophilic drug, benzocaine. In vitro permeation studies have shown that these polymer/peptide hybrids are able to produce a steady release of benzocaine over periods of up to ∼13 hours, much higher than commercially available gel formulations. Enzymatic tests have shown a significant increment in biodegradation rates in PCL/FF-MNTs hybrids containing higher peptide amounts, which exhibited almost 100% weight loss against only 10% found in pure PCL. Our findings indicate that using PCL/FF-MNTs materials is a simple route towards achieving enhanced mechanical strength of PCL networks that have the ability to promote controlled drug delivery from a completely biodegradable matrix.

Self-assembled L,L-diphenylalanine (FF) nanostructures offer an attractive platform for photonics and nonlinear optics. The nonlinear optical (NLO) coefficients of FF nanotubes depend on the diameter of the tube [S. Khanra et al. Phys. Chem. Chem. Phys. 19(4), 3084–3093 (2017)]. To further enhance the NLO properties of FF, we search for structural modifications. Here, we report on the synthesis of fluorinated FF dipeptides by replacing one ortho-hydrogen atom in each of the phenyl groups of FF by a fluorine atom. Density-functional theoretical calculations yield insights into minimum energy conformers of fluorinated FF (Fl-FF). Fl-FF self-assembles akin to FF into micron-length tubes. The effects of fluorination are evaluated on the piezoelectric response and nonlinear optical properties. The piezoelectric d15 coefficient of Fl-FF is found to be more than 10 times higher than that of FF nanotubes, and the intensity of second harmonic generation (SHG) polarimetry from individual Fl-FF nanotubes is more than 20 times that of individual FF nanotubes. Furthermore, we obtain SHG images to compare the intensities of FF and Fl-FF tubes. This work demonstrates the potential of fluorine substitution in other self-assembled biomimetic peptides for enhancing nonlinear optical response and piezoelectricity.Self-assembled L,L-diphenylalanine (FF) nanostructures offer an attractive platform for photonics and nonlinear optics. The nonlinear optical (NLO) coefficients of FF nanotubes depend on the diameter of the tube [S. Khanra et al. Phys. Chem. Chem. Phys. 19(4), 3084–3093 (2017)]. To further enhance the NLO properties of FF, we search for structural modifications. Here, we report on the synthesis of fluorinated FF dipeptides by replacing one ortho-hydrogen atom in each of the phenyl groups of FF by a fluorine atom. Density-functional theoretical calculations yield insights into minimum energy conformers of fluorinated FF (Fl-FF). Fl-FF self-assembles akin to FF into micron-length tubes. The effects of fluorination are evaluated on the piezoelectric response and nonlinear optical properties. The piezoelectric d15 coefficient of Fl-FF is found to be more than 10 times higher than that of FF nanotubes, and the intensity of second harmonic generation (SHG) polarimetry from individual Fl-FF nanotubes is more tha...

Controlling polarization in ferroelectric oxides has enabled fast switching and low-power operation in metal-oxide-semiconductor field-effect transistors (MOSFETs). Parallel studies on the performance of ferroelectric-polymer-based organic FETs (OFETs), where the polarization direction is rotated by 90\ifmmode^\circ\else\textdegree\fi{}, are lacking. This article examines the effects of external electrical poling on the performance of small-molecule OFETs. The overall transistor properties are enhanced when the ferroelectric layer is vertically poled, and are easily and reversibly controlled by switching the polarization direction. The results highlight further design principles for improving charge transport in OFETs.

Peptide-based nanostructures derived from natural amino acids are superior building blocks for biocompatible devices as they can be used in a bottom-up process without the need for expensive lithography. A dense nanostructured network of l,l-diphenylalanine (FF) was synthesized using the solid-vapor-phase technique. Formation of the nanostructures and structure-phase relationship were investigated by electron microscopy and Raman scattering. Thin films of l,l-diphenylalanine micro/nanostructures (FF-MNSs) were used as the dielectric layer in pentacene-based field-effect transistors (FETs) and metal-insulator-semiconductor diodes both in bottom-gate and in top-gate structures. Bias stress studies show that FF-MNS-based pentacene FETs are more resistant to degradation than pentacene FETs using FF thin film (without any nanostructures) as the dielectric layer when both are subjected to sustained electric fields. Furthermore, it is demonstrated that the FF-MNSs can be functionalized for detection of enzyme-analyte interactions. This work opens up a novel and facile route toward scalable organic electronics using peptide nanostructures as scaffolding and as a platform for biosensing.

Enhancing Raman signatures of molecules by self-assembled metal nanoparticles, nanolithography patterning, or by designing plasmonic nanostructures is widely used for detection of low abundance biological systems. Self-assembled peptide nanostructures provide a natural template for tethering Au and Ag nanoparticles due to its fractal surface. Here, we show the use of L,L-diphenylalanine micro-nanostructures (FF-MNSs) for the organization of Ag and Au nanoparticles (Nps) and its potential as surface-enhanced Raman scattering (SERS)-active substrates. The FF-MNSs undergo an irreversible phase transition from hexagonally packed (hex) micro-nanotubes to an orthorhombic (ort) structure at ∼150 °C. The metal Nps form chains on hex FF-MNSs as inferred from transmission electron microscopy images and a uniform non-aggregated distribution in the ort phase. The high luminescence from the ort FF-MNS phase precludes SERS measurements with AgNps. The calculated Raman spectra using density-functional theory shows a higher intensity from rhodamine 6G (R6G) molecule in the presence of an Ag atom bound to ort FF compared with hex FF. The SERS spectra obtained from R6G bound to FF-MNSs with AuNps clearly show a higher enhancement for the ort phase compared with hex FF, corroborating our theoretical calculations. Our results indicate that FF-MNSs both in the hex and ort phases can be used as substrates for the SERS analysis with different metal nanoparticles, opening up a novel class of optically active bio-based substrates.

The ferroelectric nature of polymer ferroelectrics such as poly(vinylidene fluoride) (PVDF) has been known for over 45 years. However, its role in interfacial transport in organic/polymeric field-effect transistors (FETs) is not that well understood. Dielectrics based on PVDF and its copolymers are a perfect test-bed for conducting transport studies where a systematic tuning of the dielectric constant with temperature may be achieved. The charge transport mechanism in an organic semiconductor often occurs at the intersection of band-like coherent motion and incoherent hopping through localized states. By choosing two small molecule organic semiconductors - pentacene and 6,13 bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) – along with a copolymer of PVDF (PVDF-TrFe) as the dielectric layer, the transistor characteristics are monitored as a function of temperature. A negative coefficient of carrier mobility is observed in TIPS-pentacene upwards of 200 K with the ferroelectric dielectric. In contrast, TIPS-pentacene FETs show an activated transport with non-ferroelectric dielectrics. Pentacene FETs, on the other hand, show a weak temperature dependence of the charge carrier mobility in the ferroelectric phase of PVDF-TrFE, which is attributed to polarization fluctuation driven transport resulting from a coupling of the charge carriers to the surface phonons of the dielectric layer. Further, we show that there is a strong correlation between the nature of traps in the organic semiconductor and interfacial transport in organic FETs, especially in the presence of a ferroelectric dielectric.

Self-assembled L,L-diphenylalanine (FF) peptide micro/nanotubes represent a class of biomimetic materials with a non-centrosymmetric crystal structure and strong piezoelectricity. The peptide nanotubes synthesized by a liquid phase method yield tube lengths in the hundreds of micron range, inner diameters in the few hundred nanometer range, and outer diameters in the 5–15 μm range. Second harmonic generation (SHG) polarimetry from individual self-assembled FF nanotubes is used to obtain the nonlinear (NLO) optical coefficients as a function of the tube diameter and thermal treatment. The ratio of the shear to the longitudinal component (d15/d33) of the NLO coefficient increases with the diameter of the tubes. One of the transverse components of the nonlinear coefficient is found to be negative, and its magnitude with respect to the longitudinal component increases with the tube diameter. Thermal treatment of individual FF tubes has a similar effect upon increasing the diameter of the tubes in SHG polarimetry. Concurrent Raman scattering measurements from individual FF tubes show a distinct change in the low frequency (100 cm−1) region with the diameter of the tubes reflecting subtle effects of water.

The role of high pressure on a low molecular weight nematic liquid crystalline organic semiconductor, ethyl-hexyl substituted polyfluorene (PF2/6) is investigated using photoluminescence (PL), Raman scattering, and X-ray scattering studies at pressures from 1 to 8 GPa. The PL and the Raman data under pressure are consistent with each other with no abrupt changes in the pressure coefficients of PL or Raman peaks. The PL energies redshift and broaden, consistent with both enhanced intra- and interchain interactions. The Raman peak positions yield pressure coefficients similar to other phenyl based π-conjugated polymers. The broadening of a doublet peak in the 1135 cm−1 region indicates a more planar backbone conformation with increasing pressure. X-ray scattering indicates that the torsion angle between adjacent repeats reduces with increasing pressure and reverts back with decompression. The intermolecular structure is weakly ordered (frozen nematic) and essentially maintained with increasing pressure, in contrast to a high molecular weight PF2/6. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1014–1023

Classical methods for enhancing the electromagnetic field from substrates for spectroscopic applications, such as surface-enhanced Raman spectroscopy (SERS), have involved the generation of hotspots through directed self-assembly of nanoparticles or by patterning nanoscale features using expensive nanolithography techniques. A novel large-area, cost-effective soft lithographic technique involving glancing angle deposition (GLAD) of silver on polymer gratings is reported here. This method produces hierarchical nanostructures with high enhancement factors capable of analyzing single-molecule SERS. The uniform ordered and patterned nanostructures provide extraordinary field enhancements that serve as excitatory hotspots and are herein interrogated by SERS. The high spatial homogeneity of the Raman signal and signal enhancement over a large area from a self-assembled monolayer (SAM) of 2-naphthalenethiol demonstrated the uniformity of the hotspots. The enhancement was shown to have a critical dependence on the underlying nanostructure via the surface energy landscape and GLAD angles for a fixed deposition thickness, as evidenced by atomic force microscopy and scanning electron microscopy surface analysis of the substrate. The nanostructured surface leads to an extremely concentrated electromagnetic field at sharp nanoscale peaks, here referred to as 'nano-protrusions', due to the coupling of surface plasmon resonance (SPR) with localized SPR. These nano-protrusions act as hotspots which provide Raman enhancement factors as high as 108 over a comparable SAM on silver. Comparison of our substrate with the commercial substrate Klarite™ shows higher signal enhancement and minimal signal variation with hotspot spatial distribution. By using the proper plasmon resonance angle corresponding to the laser source wavelength, further enhancement in signal intensity can be achieved. Single-molecule Raman spectra for rhodamine 6G are obtained from the best SERS substrate (a GLAD angle of 60°). The single-molecule spectrum is invariant over the substrate, due to the patterned ordered nanostructures (nano-protrusions).

Despite much study of the general mechanism of transport in organic transistors, their $p\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}l\phantom{\rule{0}{0ex}}a\phantom{\rule{0}{0ex}}r\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}z\phantom{\rule{0}{0ex}}a\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}n-d\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}m\phantom{\rule{0}{0ex}}i\phantom{\rule{0}{0ex}}n\phantom{\rule{0}{0ex}}a\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}e\phantom{\rule{0}{0ex}}d$ transport is still not well understood. Using a ferroelectric polymer for the dielectric layer in an organic field-effect transistor (OFET) allows tuning of polarization strength with temperature. Remarkably, at 200 K TIPS-pentacene OFETs with a ferroelectric dielectric exhibit a negative coefficient of mobility (bandlike transport, reminiscent of a metal, instead of the usual activated transport). The key to this behavior is the discrete nature of the trapping levels in TIPS-pentacene, and presumably other solution-processable $\ensuremath{\pi}$-conjugated conductors.

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, Al 2O 3, 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 Al 2O 3, 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.

Hybrid optoelectronic device structures offer promising options for a wide range of properties. The functioning of hybrid-bilayer devices is largely determined by their interface. Hybrid-bilayer devices based on wide band gap gallium nitride (GaN) and low band-gap donor/acceptor polymers offer a unique combination and model interface systems for application in photodetectors. A systematic study of the optoelectronic properties, specifically the photocurrent as a function of voltage bias and incident wavelength, has been carried out for n-Gan/polymer bilayer structures. A clear evidence of interface polarization originating from the GaN surface manifests in the current–voltage characteristics and photocurrent response of the hybrid structure.

We present X-ray scattering data from helical poly[9,9-bis(2-ethylhexyl)-fluorene-2,7-diyl] by mapping the sample with 10 mu m spatial resolution at pressures up to 31 GPa. Neon is used as pressure transmitting medium. Reduction of torsion angle between adjacent repeats is observed during compression and found to be reversible upon decompression. Chain conformation does not depend on lateral position of sample in the pressure range from 1 to 7 GPa but depends significantly when pressure is increased from 7 to 31 GPa. Crystallite orientation does not depend on pressure or lateral position. The radiation damage is studied optically ex situ and proved to be insignificant.

A novel enzymatic platform for the sensing of H2O2 and glucose that uses L,L-diphenylalanine micro/nanostructures (FF-MNSs) as an enzyme support is shown. This platform is obtained by the self-assembly of poly(allylamine hydrochloride) (PAH), FF-MNSs, and microperoxidase-11 (MP11) anchored onto the peptide matrix, in two different crystal structures of FF-MNSs: hexagonal (P61) and orthorhombic (P22121). The electroactive area of the electrodes increases in the presence of FF-MNSs. We also demonstrate via theoretical calculations that the valence band energy of the orthorhombic structure allows it to be doped, similarly to p-type semiconductors, where PAH acts as a doping agent for the orthorhombic peptide structure, decreasing the band-gap by around 1 eV, which results in a smaller charge transfer resistance. These results are consistent with electrochemical impedance spectroscopy measurements, which further elucidate the role of the band structure of the orthorhombic FF-MNSs in the conductivity and electron transfer rates of the hybrid material. An effective communication between the electrode and the active site of a glucose oxidase enzyme through MP11–protein complexes occurs, paving the way for FF-MNSs in the orthorhombic phase for the future development of bioelectronics sensing devices.

Matrix-assisted pulsed-laser evaporation (MAPLE) provides a mechanism for layer-by-layer growth to control the polymer–dielectric interface in organic metal–insulator–semiconductor (MIS) diodes and field-effect transistors (FETs). MAPLE-deposited copolymers of polyfluorene (PF) and polythiophene maintain their structural and optical properties, as determined by Raman spectroscopy, absorption, and photoluminescence. These films are further utilized in MIS and FET structures with SiO2 and other polymer dielectrics. Since common polymer dielectrics prevent spin coating of solution processable polymers due to solubility effects, MAPLE is one of the only deposition techniques for investigating all polymer semiconductor-insulator interfaces. In this paper we present optical and electrical studies of MAPLE-deposited PF and polythiophene films in FETs and MIS structures. The FET carrier mobilities of these devices compare well with spin-coated devices. Capacitance–voltage and conductance–voltage from MIS structures with MAPLE-deposited PF copolymer films yield interface trap densities in the low 1012 eV−1 cm−2 range.

The electrical properties of matrix-assisted pulsed-laser evaporated (MAPLE) 9,9-dioctylfluorene-co-bis-N-N-(4-butylphenyl)-bis-N,N-phenyl 1,4-phenylenediamine (PFB)-based bottom-gate organic field-effect transistors (FETs) and metal–insulator–semiconductor (MIS) diodes with poly (methyl methacrylate) (PMMA) as the dielectric layer have been investigated. The device characteristics were found to improve with an increase in the difference between the solubility parameters of PMMA and solvent. Shifts in flat band voltage of the MIS diodes were found to be due to the difference in the density of trapped holes located at the semiconductor–insulator interface. The threshold voltage of the FETs were correlated with differences in acceptor doping density and flat band voltage shifts of the MIS diodes, thereby demonstrating the role of interface traps in determining the electrical properties of organic devices. Electrical characterization of the FET shows the device to have a hysteresis-free operation in its transfer characteristics, a low threshold voltage of −0.2 V, and a field-effect mobility of 0.2 × 10−4 cm2 V−1 s−1. Interface trap states of the MIS diodes were found to be distributed in energy with their density decreasing non-linearly from approximately 2.8 × 1012 to 1.2 × 1012 eV−1 cm−2 over an energy range of 0.075–0.385 eV above the bulk Fermi level. Non-orthogonality of the semiconductor solvent had no deleterious effects on the underlying PMMA dielectric layer even without any high temperature baking, thus demonstrating that MAPLE is a viable technique for fabricating polymer dielectric-based devices and for improving the semiconductor–insulator interface.

Matrix assisted pulsed laser evaporation (MAPLE) allows homogeneous film coverage of organic materials for layer-by-layer growth providing a tighter control of the polymer–dielectric interface in field-effect transistors (FETs) and metal–insulator–semiconductor (MIS) diodes. Electrical characteristics of FETs and MIS diodes using MAPLE and spin-coated grown fluorene copolymer films are compared. Current–voltage characteristics of MAPLE grown FETs without any surface modification show a better performance compared to the spin-coated FETs. Capacitance–voltage and conductance–voltage investigations of the MIS structures show that loss as well as accumulation capacitance and time constant dispersions are less in the MAPLE grown film compared to the spin-coated film.

Polyfluorenes (PFs) represent a unique class of poly para-phenylene based blue-emitting polymers with intriguing structure-property relationships. Slight variations in the choice of functionalizing side chains result in dramatic differences in the inter- and intra-chain structures in PFs. We present photoluminescence (PL) and Raman scattering studies of bulk samples and thin films of dioctyl-substituted PF (PF8) under hydrostatic pressure. The bulk sample was further thermally annealed at 1.9 GPa. The PL vibronics of the as-is sample red-shift at an average rate of 26 meV/GPa. The thermally annealed sample is characterized by at least two phase transitions at 1.1 GPa and 4.2 GPa, each of which has a different pressure coefficient for PL vibronics. The Huang-Rhys factor, a measure of the electron-phonon interaction, is found to increase with increasing pressures signaling a higher geometric relaxation of the electronic states. The Raman peaks harden with increasing pressures; the intra-ring C-C stretch frequency at 1600 cm$^{-1}$ has a pressure coefficient of 7.2 cm$^{-1}$/GPa and exhibits asymmetric line shapes at higher pressures, characteristic of a strong electron-phonon interaction. The optical properties of PF8 under high pressure are further contrasted with those of a branched side chain substituted PF., Comment: 22 pages, 10 figures

Two new donor-acceptor type liquid crystalline semiconductors based on benzothiazole have been synthesized. Their structural, photophysical and electronic properties were investigated using X-ray diffraction, atomic force microscopy, cyclic voltammetry, UV-Vis, photoluminescence, and Raman spectroscopy. The liquid crystalline behaviour of the molecules was thoroughly examined by differential scanning calorimetry (DSC) and optical polarizing microscope. The DSC and thermogravimetric analysis (TGA) show that these materials posses excellent thermal stability and have decomposition temperatures in excess of 300 degrees C. Beyond 160 degrees C both molecules show a smectic A liquid crystalline phase that exists till about 240 degrees C. Field-effect transistors were fabricated by vacuum evaporating the semiconductor layer using standard bottom gate/top contact geometry. The devices exhibit p-channel behaviour with hole mobilities of 10(-2) cm(2)/Vs. (C) 2009 Elsevier B.V. All rights reserved.