In-plane Carrier Research Articles

Controlling the Thermoelectric Performance of Doped Naphthobisthiadiazole-Based Donor-Acceptor Conjugated Polymers through Backbone Engineering.

This study investigates backbone engineering and evaluates the thermoelectric properties of FeCl3-doped naphthobisthiadiazole (NTz)-based donor-acceptor (D-A) conjugated polymer films. The NTz acceptor unit is coupled with three distinct donor units, namely dialkylated terthiophene (3T), dialkylated quaterthiophene (4T), and dialkylated bisthienyl thienothiophene (2T-TT) to yield copolymers designated as PNTz3T, PNTz4T, and PNTzTT. The difference in donor units leads to diverse molecule stacking and electronic properties, which can be systematically discovered via the three polymers. The linear structure of PNTz4T enables an orderly arrangement of side chains, thereby promoting dopant intercalation for enhanced carrier concentration. Additionally, this linear structure leads to an edge-on stacking mode, thereby improving the in-plane carrier mobility. As a result, the doped PNTz4T exhibits the highest electrical conductivity (σ) of 88.3 S cm-1 along with a Seebeck coefficient (S) of 62.2 µV K-1, thereby achieving the highest power factor (PF) of 34.2 µW m-1 K-2. These results highlight the relationship between the molecular design, microstructure, and doping effects in manipulating the thermoelectric performance of doped NTz-based D-A polymers.

Electron Transport over 2D Molecular Materials and Assemblies.

ConspectusTwo-dimensional (2D) molecular materials, in which the major interactions are confined in 2D planes with contrasted force fields acting in between the planes, have been key electronic functional materials since the past decade. Even without referring to the functionals of graphene-based systems, 2D electronic conjugated systems are expected to show extrawide dynamic ranges in electronic density of states (DOS) tuning, effective electron mass, electron mobility, and conductivity. A major advantage of 2D electronic systems is their compatibility with the ubiquitous electronic devices designed using planar structures, such as transistors and memories, which is associated with the utility of 2D active materials. The mobility of electrons in 2D systems is the key to their utility, and various conjugated molecular and 2D materials have been designed to optimize the mobility. This Account begins with an introduction for mobility assessment: using noncontact time-resolved microwave conductivity (TRMC) measurements as a technique to probe differential conductivity upon transient charge carrier injection into the materials. Electronic transport over 2D electronic materials such as graphenes, covalent organic frameworks (COFs), and metal-organic frameworks (MOFs) is discussed with a special emphasis on molecular building blocks, fine-tuning conducting species and linkages, topology of the framework, and controlling molecular doping. The superiority of β-ketoenamine-linked COF over imine-linked COF films in charge transport and dominant in-plane charge carrier mobility over out-of-plane mobility is also illustrated. Systematic molecular engineering of the building blocks of β-ketoenamine-linked COFs with varying degrees of donor-acceptor (D-A) conjugation, torsional angles, and reaction conditions resulted in the modulation of the efficiency of charge carrier generation/transport as well as exciton migration. The advantages of 2D systems are finally discussed in terms of the mobility interplaying with spatial arrangements of molecules as well as the substantial role of intermolecular interactions in stabilizing their condensed phases. The strong correlation between the dispersion of mobility and hierarchical intermolecular interactions sheds light on the way to overcome structural fluctuation on the optimization of charge transport in molecular electronic materials. The point of singularity in the dispersion at an intermolecular distance of d ∼ 0.3 nm is deduced from the overall mobility assessment in condensed phases of conjugated molecules, suggesting key roles of intermolecular electronic coupling: the new concept of electronic conjugation. Exceptional electronic coupling with relatively high charge carrier mobility was also observed, particularly in 2D spatial arrangements of chiral molecules in contrast to 3D analogues, where the reduction of gravitational density of the molecular condensates was impacting DOS: the Wallach's rule. 2D electronic systems are strong candidates for the violation of the long-lasting Wallach's rule in terms of DOS.

Understanding the effect of multiple configurations in polymeric carbon nitride for efficient solar-driven hydrogen peroxide photosynthesis

A oxygen and potassium co-doped polymeric carbon nitride (O/K-PCNs) was simply constructed by an acid gas cutting strategy for photocatalytic H2O2 generation. The effect of each accompanied configurations on photosynthesis of H2O2 was systematically analyzed. The C–O–C structure formed by O doping is capable of decreasing K ions incorporated energy barrier, thus remarkably improving the content of crucial K active sites. Dual heteroatom sites synergistically enhance O2 adsorption and surface ORR by a bridge K–O–O–C model. Moreover, the accompanied cyano defect and poly(heptazine imide) is responsible for improving in-plane and interlayer carriers separation, respectively. The optimal O/K-PCNs exhibits 60-fold higher photocatalytic H2O2 production rate than pure PCN. A positive correlation between the H2O2 production rate and the K heteratoms content was established. This work clarifies role of multiple configurations in PCN, especially O-containing groups, providing a new insight for design heteroatoms-doped materials for solar energy conversion.

Interaction of in-plane Drude carrier with c-axis phonon in PdCoO2

We performed polarized reflection and transmission measurements on the layered conducting oxide PdCoO2 thin films. For the ab-plane, an optical peak near Ω ≈ 750 cm−1 drives the scattering rate 1/τ(ω) and effective mass m*(ω) of the Drude carrier to increase and decrease respectively for ω ≧ Ω. For the c-axis, a longitudinal optical phonon (LO) is present at Ω as evidenced by a peak in the loss function Im[−1/εc(ω)]. Further polarized measurements in different light propagation (q) and electric field (E) configurations indicate that the Peak at Ω results from an electron-phonon coupling of the ab-plane carrier with the c-LO phonon, which leads to the frequency-dependent 1/τ(ω) and m*(ω). This unusual interaction was previously reported in high-temperature superconductors (HTSC) between a non-Drude, mid-infrared (IR) band and a c-LO. On the contrary, it is the Drude carrier that couples in PdCoO2. The coupling between the ab-plane Drude carrier and c-LO suggests that the c-LO phonon may play a significant role in the characteristic ab-plane electronic properties of PdCoO2, including the ultra-high dc-conductivity, phonon-drag, and hydrodynamic electron transport.

In-plane carrier regulation and hydrogen adsorption/desorption optimization of P4 molecule anchored Vs-ZnIn2S4−x for improve photocatalytic activity

Molecular-type cocatalysts can achieve the maximum electron transfer and minimum light absorption loss by virtue of their size advantage. Herein, a novel hydrophilic molecule-semiconductor hybrid P4@Vs-ZnIn2S4−x photocatalyst was successfully developed by in-situ P4 molecular anchoring on S defect ZnIn2S4−x (VS-ZnIn2S4−x). The electron-rich P4 molecules are anchored on the Zn-S4 surface through S vacancies, forming Zn-P and S-P bonds that can promote electron injection from the electron-rich P4 molecular to Vs-ZnIn2S4−x substrate and reduce the adsorption/desorption barrier of H intermediate on S atom of Zn-S4 plane. Meanwhile, the electrostatic potential depression around P4 promoted the directional migration of in-plane photogenerated electrons, and pooled electrons to the highly active P sites and S sites, thereby accelerating the kinetics of hydrogen evolution. As a result, P4@Vs-ZnIn2S4−x achieves an optimal photocatalytic hydrogen evolution activity of 26.1 mmol g−1 h−1 under visible light, which is 6.2 times higher than 4.2 mmol g−1 h−1 for Vs-ZnIn2S4−x.

Regulation of sulfur vacancies in vertical nanolamellar MoS2 for ultrathin flexible piezoresistive strain sensors

• The vertical MoS 2 nanosheets prepared by magnetron sputtering displayed a piezoresistive effect, which has not been reported previously. • Contact and separation of channels between the vertical MoS 2 nanosheets under strain, leading to excellent piezoresistive properties. • Sulfur vacancies enhance electron transport of in-plane MoS 2 nanosheets. • The flexible sensors were excellent in human motion and bionic flight monitoring. Magnetron-sputtered MoS 2 has applications in piezoresistive functional materials research owing to its unique nanostructure. However, the controlled incorporation of sulfur vacancies and realization of enhanced piezoresistive performance remain significant challenges. In this work, the direct growth of large-area MoS 2 films with tunable sulfur vacancy concentrations was successfully achieved via magnetron sputtering at various temperatures. Microstructural analysis revealed that the application of strain altered the number of conductive channels between the vertical MoS 2 nanosheets, changing the measured resistance and leading to excellent piezoresistive properties. More importantly, the unsaturated electrons due to the sulfur vacancies increased the in-plane carrier concentration of the MoS 2 nanosheets. A deposition temperature of 50°C afforded the highest concentrations of sulfur vacancies and carriers. These MoS 2 films possessed a carrier concentration of 6.58 × 10 17 cm −3 , which was 40.9% higher than that obtained at 150°C, and displayed superior piezoresistive performance. The films exhibited high gauge factors of 2.66 and 23.22 under tensile and compressive strain of ≤0.29%, respectively. These values were 118% and 323% higher, respectively, than those obtained for films deposited at 150°C. This work provides an effective route for modulating and mass producing MoS 2 -based piezoresistive electronic devices.

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

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

Two-dimensional ferromagnetic semiconductors of rare-earth Janus 2H-GdIBr monolayers with large valley polarization.

Based on a rare-earth Gd atom with 4f electrons, through first-principles calculations, we demonstrate that a Janus 2H-GdIBr monolayer exhibits an intrinsic ferromagnetic (FM) semiconductor character with an indirect band gap of 0.75 eV, a high Curie temperature Tc of 260 K, a significant magnetic moment of 8μB per f.u. (f.u. = formula unit), in-plane magnetic anisotropy (IMA) and a large spontaneous valley polarization of 118 meV. The MAE, inter-atomic distance or angle, and Tc can be efficiently modulated by in-plane strains and charge carrier doping. Under a strain range from -5% to 5% and charge carrier doping from -0.3 e to 0.3 e per f.u., the system still retains its FM ordering and the corresponding Tc can be modulated by strains from 233 K to 281 K and by charge carrier doping from 140 K to 245 K. Interestingly, under various strains, the matrix element differences (dz2, dyz), (dx2-y2, dxy) and (px, py) of Gd atoms dominate the MAE behaviors, which originates from the competition between the contributions of the Gd-d orbitals, Gd-p orbitals, and p orbitals of halogen atoms based on the second-order perturbation theory. Inequivalent Dirac valleys are not energetically degenerate due to the time-reversal symmetry breaking in the Janus 2H-GdIBr monolayer. A considerable valley gap between the Berry curvature at the K and K' points provides an opportunity to selectively control the valley freedom and states. External tensile (compressive) strain further increases (decreases) the valley gap up to a maximum (minimum) value of 158 (37) meV, indicating that the valley polarization in the Janus 2H-GdIBr monolayer is robust to external strains. This study provides a novel paradigm and platform to design spintronic devices for next-generation quantum information technology.

Realizing high in-plane carrier mobility in n-type SnSe crystals through deformation potential modification

The in-plane carrier mobility in n-type SnSe crystals increases to ∼445 cm2 V−1 s−1 due to the decreased deformation potential by Pb alloying, demonstrating the thermoelectric cooling potential of n-type SnSe crystals.

SnSe crystalline thermoelectrics

Thermoelectric materials are increasingly crucial in addressing energy challenges for enabling conversion between heat and electricity. Crystalline tin selenide (SnSe) has gained significant attention since 2014 when its high-temperature thermoelectric performance was first reported. Based on unique characteristics in phonon and electron transports, numerous investigations have been conducted to promote the development of SnSe crystals for low- to mid-temperature waste recovery and electronic cooling applications. Herein, we concisely summarize the significant advancements for SnSe crystalline thermoelectrics, covering material performance optimization and full-scale thermoelectric device development. We then emphasize that the multiple valence bands and high in-plane carrier mobility achieved high-performance p-type materials. Additionally, we highlight the critical role of three-dimensional (3D) charge and two-dimensional (2D) phonon transports for promising n-type out-of-plane conduction. Finally, personal insights into future research directions of enhancing performance of SnSe materials and devices are proposed, with the goal of advancing their practical applications.

Electric-Field-Tunable Spin Polarization and Carrier-Transport Anisotropy in an A-Type Antiferromagnetic van der Waals Bilayer

Two-dimensional (2D) magnetic semiconductor materials with the electric-field-tunable spin polarization and carrier-transport anisotropy are of great significance for the fundamental physics and device application. Here we propose a general strategy to tune the spin polarization and anisotropic effective mass in a 2D A-type antiferromagnetic (AFM) bilayer system. We take the A-type AFM bilayer $\mathrm{CrSBr}$ (with the intralayer ferromagnetic and interlayer AFM coupling) as an example to confirm this design principle. Firstly, a vertical electric field can lift the spin degeneracy in the A-type AFM bilayer $\mathrm{CrSBr}$. By flipping the direction of electric field, the spin polarization direction can be reversed. Secondly, in the A-type AFM bilayer $\mathrm{CrSBr}$ with an interlayer twist angle of 90\ifmmode^\circ\else\textdegree\fi{}, both the spin direction and the carrier-transport anisotropy can be tuned simultaneously by applying a vertical electric field due to the in-plane anisotropic carrier effective mass in each $\mathrm{CrSBr}$ monolayer. This opens an opportunity for controlling the spin polarization as well as carrier-transport anisotropy in the 2D magnetic van der Waals layered materials by interlayer twist and electric field, and provides an idea for utilizing A-type AFM semiconductors to design spintronic devices.

Multilayered Alternating-Cations-Intercalation Chiral Hybrid Perovskites with High Circular Polarization Sensitivity.

Multilayered chiral hybrid perovskites are highly desired for highly-sensitive circularly polarized light (CPL) detection rooted in their efficient charge transport and strong chiroptical activity. However, designing multilayered chiral hybrid perovskites remains a huge challenge. Here, through pairing achiral ethylamine (EA)-chiral arylamine in the interlayer space, multilayered chiral alternating cations intercalation-type (ACI) hybrid perovskites (R-/S-PPA) EA2 Pb2 Br7 (PPA = 1-phenylpropylamine) are successfully obtained. Significantly, perovskitizer EA extends the thickness of the quantum well and alternating space cation EA greatly alleviates in-plane tilting distortions of adjacent metal halide octahedra, providing fast channels for in-plane carrier transport. Consequently, single-crystal photodetectors of (R-/S-PPA) EA2 Pb2 Br7 exhibit high circular polarization sensitivity with a large anisotropy factor of 0.3, which falls around the highest value among the layered hybrid perovskites. In addition, a fast responding rate (τr )of 308 µs and a high CPL-detectivity of 8× 1012 Jones are also presented. This work opens up a new perspective to design multilayered chiral hybrid perovskites for high-sensitive CPL detection.

Femtosecond Laser Fabrication of Anisotropic Structures in Phosphorus- and Boron-Doped Amorphous Silicon Films.

Femtosecond laser-modified amorphous silicon (a-Si) films with optical and electrical anisotropy have perspective polarization-sensitive applications in optics, photovoltaics, and sensors. We demonstrate the formation of one-dimensional femtosecond laser-induced periodic surface structures (LIPSS) on the surface of phosphorus- (n-a-Si) and boron-doped (p-a-Si) amorphous silicon films. The LIPSS are orthogonal to the laser polarization, and their period decreases from 1.1 ± 0.1 µm to 0.84 ± 0.07 µm for p-a-Si and from 1.06 ± 0.03 to 0.98 ± 0.01 for n-a-Si when the number of laser pulses per unit area increases from 30 to 120. Raman spectra analysis indicates nonuniform nanocrystallization of the irradiated films, with the nanocrystalline Si phase volume fraction decreasing with depth from ~80 to ~40% for p-a-Si and from ~20 to ~10% for n-a-Si. LIPSS' depolarizing effect, excessive ablation of the film between LIPSS ridges, as well as anisotropic crystalline phase distribution within the film lead to the emergence of conductivity anisotropy of up to 1 order for irradiated films. Current-voltage characteristic nonlinearity observed for modified p-a-Si samples may be associated with the presence of both the crystalline and amorphous phases, resulting in the formation of potential barriers for the in-plane carrier transport and Schottky barriers at the electric contacts.

Ultralow In-Plane Thermal Conductivity in 2D Magnetic Mosaic Superlattices for Enhanced Thermoelectric Performance.

Lowering thermal conductivity via introducing heterointerfaces of heterophase fillings (HPFs) is a common strategy for optimizing thermoelectric performance, but it is always accompanied by deterioration of electrical conductivity. Here we report an ordered magnetic HPF system in a CoSe2-SnSe mosaic heterostructure superlattice synthesized by van der Waals confined epitaxial growth (vdWCEG), which realizes a maximized filling amount to decrease in-plane thermal conductivity of SnSe layers and maintain the intact in-plane carrier transport path. The in-plane thermal conductivity of CoSe2-SnSe superlattice reaches the lowest range among SnSe-based materials with a value of 0.27 W m-1 K-1 at 850 K, which can be attributed to abundant interfaces between CoSe2 nanocrystals and SnSe layers. Moreover, the CoSe2 nanocrystals show superparamagnetic behavior, by which the rotation of magnetic domains provides additional phonon scattering to further decrease in-plane thermal conductivity. By combination with the preserved in-plane electrical conductivity of SnSe layers, an enhanced in-plane ZT value of 0.62 is achieved at 850 K. This vdWCEG approach can also be generally applied to fabricate various other two-dimensional (2D) mosaic heterostructures, providing an avenue for artificial 2D heterostructures with desired functionalities.

Defect-assisted tunneling spectroscopy of electronic band structure in twisted bilayer graphene/hexagonal boron nitride moiré superlattices

We report the demonstration of defect-assisted tunneling spectroscopy of the electronic band structure in twisted bilayer graphene (tBLG)/hexagonal boron nitride (h-BN) moiré superlattices in which the moiré period between the two graphene layers is close to that between the graphene and h-BN layers. We measured both the in-plane and vertical carrier transport in the tBLG/h-BN van der Waals (vdW) tunneling device. The moiré periods were determined from the in-plane carrier transport measurements. The observed vertical tunneling transport characteristics indicated that resonant tunneling occurs from the graphite electrode to tBLG through localized defect states in the h-BN tunnel barrier. We observed multiple defect-assisted resonant tunneling trajectories, from which we derived the density of states (DOS) for tBLG. The obtained DOS has broad flatband features, in qualitative agreement with the theoretical predictions. Furthermore, we obtained three types of DOS, suggesting that we probed local band structures corresponding to AA, AB/BA, and domain wall sites in tBLG. Thus, defect-assisted tunneling spectroscopy has potential as a tool to determine the local band structures in twisted 2D vdW materials.

Long carrier diffusion length in two-dimensional lead halide perovskite single crystals

<h2>Summary</h2> Ruddlesden-Popper (RP) perovskites are two-dimensional semiconductors for high-performance optoelectronic devices. In this work, we report a long in-plane carrier diffusion length in 2D RP perovskite single crystals probed by scanning photocurrent microscopy. Carrier diffusion lengths of 7–14 μm are observed when the number of PbI₆⁻² octahedra between organic spacers increases from 1 to 3. Using detailed light intensity and electric-field-dependent photocurrent measurements, we attribute the observed long diffusion length to the dominating dissociated free carrier transport. This is further validated by time-resolved photoluminescence measurements, where the decay lifetime increases in the presence of an electric field. From our experiments, we conclude that the in-plane transport in RP perovskites is efficient because of the partial free carrier generation, which overcomes strong excitonic effects. Our results suggest that semiconducting devices fabricated from RP perovskite single crystals can be as efficient as their 3D counterparts.

Vibronic States and Edge-On Oriented π-Stacking in Poly(3-alkylthiophene) Thin Films

The influence of alkyl side-chain length [CnH2n+1 (A), where n = 6 (hexyl), 8 (octyl), 12 (dodecyl)] and thermal annealing (TA) and the definite roles of these in the quantity and quality of π-stacked crystallinity and edge-on orientated (EO) ordering of spin-coated poly(3-alkylthiophene) [P3AT] thin films, which are of massive significance in their optoelectronic properties, were investigated using complementary optical absorption spectroscopy and X-ray reflectivity (XR) techniques. The energy-band diagram, corresponding to the vibronic levels, obtained from the optical absorption spectrum provides information about the percentage, planarity, local order, and average conjugation length of the crystalline aggregates, while the electron density profile obtained from the XR provides unique information about the EO ordering and its variation along the depth. A prominent EO ordering near the substrate with a gradually decreased ordering toward the top surface is observed in each film. An as-cast P3HT film of shorter side-chain (having a natural nucleation tendency and rigidity) shows a slightly higher crystallinity and weaker excitonic coupling, while as-cast P3DDT film (having longer side-chain flexibility) shows a slightly better EO ordering. After the TA, the planarity of the unfolded backbone improves in each film; however, the effect is maximum in the P3DDT film. The EO ordering also improves throughout the film (by a thermal energy-induced reorientation of crystallites) but more toward the top surface (by increasing the decay length), preserving the exponential decay nature. The P3HT film (with the better initial crystallinity and planarity) shows an appreciable improvement, while the P3DDT film (where the crystallinity increases and crystallites have a better reorientational ability) shows the maximum improvement in the EO ordering. The improvement of the crystallinity (in quantity and quality) and the EO ordering of P3AT in thin films (as active layers), especially near the film–substrate interfaces, are of immense importance for their better in-plane charge carrier mobility in a thin-film transistor.

Mechanism of In-Plane and Out-of-Plane Tribovoltaic Direct-Current Transport with a Metal/Oxide/Metal Dynamic Heterojunction.

Interfacial layer engineering has been demonstrated as an effective strategy for boosting power output in semiconductor-based dynamic direct-current (DC) generators, although the underlying mechanism of power enhancement remains obscure. Here, such ambiguity has been elucidated by comparing fundamental tribovoltaic DC output characteristics of prototypical metal-oxide-metal heterojunctions prepared by atomic-layer deposition (ALD) with a vertical (out-of-plane carrier transport through the interfacial layer) and a horizontal (in-plane carrier transport along the interfacial layer) configuration such that the influences from nonequilibrium electronic excitation and interfacial capacitive amplification can be individually tuned and investigated. It is found in the case of Al/TiO2/Ti vertical configurations that the open-circuit voltage (VOC) increases linearly from -0.03 to -0.52 V as the thickness of titanium oxide (tTiO2) increases from 0 to 200 nm with a linear amplification coefficient of -2.31 mV nm-1, which is validated by a parallel-capacitor theoretical model with tribovoltaic electronic excitation. In contrast, the VOC output with the horizontal configuration is ∼55 mV, where the potential difference is merely associated with the accumulation of surface charges and the subsequent charge rearrangement in the depletion region. Meanwhile, it is measured that the short-circuit current density (JSC) shows an initial increasing trend when tTiO2 increases, reaches its peak value at 0.21 A m-2 at tTiO2 = 20 nm, and then decreases as tTiO2 increases further. From current-voltage (I-V) characterization, it is proposed that such DC output variation with an optimal interfacial layer thickness stems from the competition of amplified voltage and increased resistance with increasing interfacial layer thickness, with the main charge transport mechanism switching from quantum tunneling to thermionic emission/trap-assisted transport. In contrast, tribovoltaic excitation is proven to be significantly weaker when a wide band-gap insulator (Al2O3) is involved. The elucidation of the fundamental mechanism of power enhancement by the interfacial layer in this work is of great significance in providing instructional direction for the development and optimization of high-performance DC nanogenerators.

Optimized Charge Transport in Molecular Semiconductors by Control of Fluid Dynamics and Crystallization in Meniscus‐Guided Coating (Adv. Funct. Mater. 2/2022)

Optimized Charge Transport In article number 2107976, Jasper J. Michels, Wojciech Pisula, Tomasz Marszalek, and co-workers identify an optimal processing window for zone-casting of a molecular semiconductor for organic fieldeffect transistors. Computational modelling of the fluid dynamics and the crystallization explains the occurrence of three morphological subregimes: i) isotropic domain-like, ii) unidirectional crystal stripes and iii) corrugated dendritic. Control of the semiconductor film morphology allows to optimize the in-plane charge carrier transport.

Manipulating Edge Current in Hexagonal Boron Nitride via Doping and Friction.

We map spatially correlated electrical current on the stacking boundaries of pristine and doped hexagonal boron nitride (hBN) to distinguish from its insulating bulk via conductive atomic force microscopy (CAFM). While the pristine edges of hBN show an insulating nature, the O-doped edges reveal a current 2 orders of higher even for bulk layers where the direct transmission through tunnel barrier is implausible. Instead, the nonlinear current-voltage characteristics (I-V) at the edges of O-doped hBN can be explained by trap-assisted lowering of the tunnel barrier by adopting a Poole-Frenkel (PF) model. However, in the stacked heterostructure with multilayer graphene (MLG) on top, the buried edge of pristine hBN shows a signature of electron conduction in the scanning mode which contradicts the first-principle calculation of spatial distribution of local density of states (LDOS) data. Enhancement of friction between the Pt-tip and MLG at the step-edge of the heterostructure while scanning in the contact mode has prompted us to construct a phenomenological model where the localization of opposite surface charges on two conducting plates (MLG and Si substrate) containing a dielectric film (hBN) with negatively charged defects creates an internal electric field opposite to the external electric field due to the applied voltage bias in the CAFM setup. An equivalent circuit with a parallel resistor network based on a vertical conducting channel through the MLG/hBN edge and an in-plane surface carrier transport through MLG can successfully analyze the current maps on pristine/doped hBN and the related heterostructures. These results yield fundamental insight into the emerging field of insulatronics in which defect-induced electron transport along the edge can be manipulated in an 1D-2D synergized insulator.