Charge Transport Measurements Research Articles

Printed Memtransistor Utilizing a Hybrid Perovskite/Organic Heterojunction Channel.

Neuromorphic computing has the potential to address the inherent limitations of conventional integrated circuit technology, ranging from perception, pattern recognition, to memory and decision-making ( Acc. Chem. Res. 2019, 52 (4), 964-974) ( Nature 2004, 431 (7010), 796-803) ( Nat. Nanotechnol. 2013, 8 (1), 13-24). Despite their low power consumption ( Nano Lett. 2016, 16 (11), 6724-6732), traditional two-terminal memristors can perform only a single function while lacking heterosynaptic plasticity ( Nanotechnology 2013, 24 (38), 382001). Inspired by the unconditioned reflex, multiterminal memristive transistors (memtransistor) were developed to realize complex functions, such as multiterminal modulation and heterosynaptic plasticity ( Nature 2018, 554, (7693), 500-504). Here we combine a hybrid metal halide perovskite with an organic conjugated polymer to form heterojunction transistors that are responsive to both electrical and optical stimuli. We show that the synergistic effects of photoinduced ion migration in the perovskite and electronic transport in the polymer layers can be exploited to realize memristive functions. The device combines reversible, nonvolatile conductance modulation with large switching current ratios, high endurance, and long retention times. Using in situ scanning Kelvin probe microscopy and variable-temperature charge transport measurement, we correlate the collective effects of bias-induced and photoinduced ion migration with the heterosynaptic behavior observed in this hybrid memtransistor. The hybrid heterojunction channel concept is expected to be applicable to other material combinations making it a promising platform for deployment in innovative neuromorphic devices of the future.

(Invited) Chemistry in a Nanoscale Gap

In the realm of the Single-Molecule Electronics, a suite of advanced electrical characterization approaches have emerged allowing measuring charge transport in an electric contact made out of an individual molecule[1]. The field has (and is still) drawn(ing) an scenario where individual molecules can be chemically modified to deliver a particular electrical function in a nanoscale circuit, e.g. variable resistors[2], diodes[3], switches[4], etc. Along this excursion, we have observed that single molecules trapped in a nanoscale tunneling junction experience conformational structural changes and changes in molecule/electrode contact geometries, which are usually accompanied by large conductance variations and can be easily detected electrically[1]. Such changes are induced by the imposed forces fields experienced by the molecules within the nanoscale gap, namely, a mechanical force and/or an electric field. In the past decade, we have learnt that under certain force field conditions, the individual molecules wired in a nanoscale junction undergo chemical transformations. Here, we will present a couple of illustrative examples of the use of single-molecule junction to study and control reactivity at the nanoscale using electric fields, a concept that is inherent in the natural enzymatic molecular machinery[5]. Tunable, well-oriented electric fields can be easily delivered along the main junction axis of a nanoscale electrical device[6]. We exploited the latter to study; (1) a simple monomolecular cis-trans isomerization reaction[7], and (2) a bi-molecular Diels-Alder reaction[8]. Along with the experimental design and fundamental chemistry aspects, we will discuss the advantages these examples can bring to possible technological applications.[1]. L. Sun et al. Chem. Soc. Rev., 2014,43, 7378-7411.[2]. A. C. Aragones et al. Chem. Eur.J.2015, 21,7716 –7720.[3]. I. Diez-Perez et al. Nature Chemistry 1, 635–641 (2009).[4]. N. Darwish et al. Nano Lett. 2014, 14, 12, 7064–7070.[5]. Stephen D. Fried et al. Annu Rev Biochem. 2017; 86: 387–415.[6]. N. Darwish et al. “Principles of Molecular Devices Operated by Electric Fields” in Effects of Electric Fields on Structure and Reactivity: New Horizons in Chemistry, Royal Society of Chemistry, Ed. Sason Shaik.[7]. C. S. Quintans et al. Appl. Sci. 2021, 11(8), 3317.[8]. A. C. Aragones et al. Nature 531, 88–91 (2016).

Mimicking Melanopsin Behavior with Integrated Photoregulated Memory

AbstractMelanopsin is an essential element in the human eye, sensing optical light, indeed beyond the function of rods and cones, and contributing largely to non‐image‐forming functions like learning behavior, emotions, and maintaining sun cycle. Mimicking melanopsin behavior using an optoelectronic device could be an essential step toward the advancement of future technologies, including data storage applications and artificial vision. This research proposes and illustrates the mimicking of the primitive functions of melanopsin in a manner very similar to the human eye retina by using an integrated Schottky photodetector and an HfO2‐based memory device. Particularly, current–voltage curves show nominal hysteresis loop opening under dark conditions, whereas stable analog hysteresis loops form with light illumination, which is regulated progressively by increasing the intensity. Based on photoconductive atomic force microscopy and charge transport measurements, the charge trapping/detrapping is estimated to be associated with the light‐regulated hysteresis loop opening. Specifically, versatile synaptic functions are stimulated artificially with an optical pulse, which is sustained over a long period of time even after removing the light, indeed very similar to melanopsin behavior. The optically regulated properties described herein pave the way for the development of artificial optoelectronic melanopsin, artificial biological electronics, soft robotics, and data storage applications.

Defect characterization and charge transport measurements in high-resolution Ni/n-4H-SiC Schottky barrier radiation detectors fabricated on 250 μm epitaxial layers

Advances in the growth processes of 4H-SiC epitaxial layers have led to the continued expansion of epilayer thickness, allowing for the detection of more penetrative radioactive particles. We report the fabrication and characterization of high-resolution Schottky barrier radiation detectors on 250 μm thick n-type 4H-SiC epitaxial layers, the highest reported thickness to date. Several 8 × 8 mm2 detectors were fabricated from a diced 100 mm diameter 4H-SiC epitaxial wafer grown on a conductive 4H-SiC substrate with a mean micropipe density of 0.11 cm−2. From the Mott–Schottky plots, the effective doping concentration was found to be in the range (0.95–1.85) × 1014 cm−3, implying that full depletion could be achieved at ∼5.7 kV (0.5 MV/cm at the interface). The current-voltage characteristics demonstrated consistently low leakage current densities of 1–3 nA/cm2 at a reverse bias of −800 V. This resulted in the pulse-height spectra generated using a 241Am alpha source (5486 keV) manifesting an energy resolution of less than 0.5% full width at half maximum (FWHM) for all the detectors at −200 V. The charge collection efficiencies (CCEs) were measured to be 98–99% with no discernable correlation to the energy resolution. A drift-diffusion model fit to the variation of CCE as a function of bias voltage, revealed a minority carrier diffusion length of ∼10 μm. Deep level transient spectroscopy measurements on the best resolution detector revealed that the excellent performance was the result of having ultralow concentrations of the order of 1011 cm−3 lifetime limiting defects—Z1/2 and EH6/7.

Multidimensional Characterization of Single-Molecule Dynamics in a Plasmonic Nanocavity.

Nanoscale manipulation and characterization of individual molecules is necessary to understand the intricacies of molecular structure, which governs phenomena such as reaction mechanisms, catalysis, local effective temperatures, surface interactions, and charge transport. Here we utilize Raman enhancement between two nanostructured electrodes in combination with direct charge transport measurements to allow for simultaneous characterization of the electrical, optical, and mechanical properties of a single molecule. This multi-dimensional information yields repeatable, self-consistent, verification of single-molecule resolution, and allows for detailed analysis of structural and configurational changes of the molecule in situ. These experimental results are supported by a machine-learning based statistical analysis of the spectral information and calculations to provide insight into the correlation between structural changes in a single-molecule and its charge-transport properties.

Multidimensional Characterization of Single‐Molecule Dynamics in a Plasmonic Nanocavity

AbstractNanoscale manipulation and characterization of individual molecules is necessary to understand the intricacies of molecular structure, which governs phenomena such as reaction mechanisms, catalysis, local effective temperatures, surface interactions, and charge transport. Here we utilize Raman enhancement between two nanostructured electrodes in combination with direct charge transport measurements to allow for simultaneous characterization of the electrical, optical, and mechanical properties of a single molecule. This multi‐dimensional information yields repeatable, self‐consistent, verification of single‐molecule resolution, and allows for detailed analysis of structural and configurational changes of the molecule in situ. These experimental results are supported by a machine‐learning based statistical analysis of the spectral information and calculations to provide insight into the correlation between structural changes in a single‐molecule and its charge‐transport properties.

(Invited) Globally Aligned, Wafer-Scale Deposition of Carbon Nanotubes Via Interfacial Assembly

Floating evaporative self-assembly (FESA) is a solution-based technique for fabricating highly-aligned semiconducting carbon nanotube films.1,2 Field-effect transistors (FETs) based on carbon nanotubes aligned via FESA have exhibited current densities exceeding that of GaAs and Si, demonstrating the promise of this technique.3 However, the global uniformity of FESA films is poor, as the films are composed of stripes of aligned and randomly oriented carbon nanotubes. Additionally, this technique is inherently difficult to scale. In the work presented here, we demonstrate a scalable technique to overcome the shortcomings of FESA and to achieve globally uniform films of aligned carbon nanotubes at desirable packing densities for FETs.In our technique, carbon nanotubes are continuously aligned across target substrates by lifting the substrates through a flowing nanotube ink/water interface. The ink/water interface collects and confines the nanotubes, which is vital to achieving a high degree of alignment. Polarized Raman spectroscopy mapping is used to quantify the degree of alignment in the resulting aligned nanotube films. The full width at half maximum (FWHM) of the alignment distribution within the films is 6.0° measured across a 1 mm2 area. We control the aligned carbon nanotube packing density from 0.2 to 59 µm-1 by varying the ink concentration from 0.1 to 100 µg mL-1. Using optimized conditions, we demonstrate the scalability of this technique by aligning carbon nanotubes across a 100 mm wide wafer. Charge transport measurements are performed using FETs with the aligned carbon nanotube films as the active channels, and the performance is compared to FETs based on FESA films.1. Jinkins, K., R. et al. Nanotube Alignment Mechanism in Floating Evaporative Self-Assembly. Langmuir 33, 13407–13414 (2017).2. Joo, Y., Brady, G. J., Arnold, M. S. & Gopalan, P. Dose-Controlled, Floating Evaporative Self-assembly and Alignment of Semiconducting Carbon Nanotubes from Organic Solvents. Langmuir 30, 3460–3466 (2014).3. Brady, G. J. et al. Quasi-ballistic carbon nanotube array transistors with current density exceeding Si and GaAs. Sci. Adv. 2, (2016).

Origin of the quasi-quantized Hall effect in ZrTe5

The quantum Hall effect (QHE) is traditionally considered to be a purely two-dimensional (2D) phenomenon. Recently, however, a three-dimensional (3D) version of the QHE was reported in the Dirac semimetal ZrTe5. It was proposed to arise from a magnetic-field-driven Fermi surface instability, transforming the original 3D electron system into a stack of 2D sheets. Here, we report thermodynamic, spectroscopic, thermoelectric and charge transport measurements on such ZrTe5 samples. The measured properties: magnetization, ultrasound propagation, scanning tunneling spectroscopy, and Raman spectroscopy, show no signatures of a Fermi surface instability, consistent with in-field single crystal X-ray diffraction. Instead, a direct comparison of the experimental data with linear response calculations based on an effective 3D Dirac Hamiltonian suggests that the quasi-quantization of the observed Hall response emerges from the interplay of the intrinsic properties of the ZrTe5 electronic structure and its Dirac-type semi-metallic character.

Role of the reorganization energy for charge transport in disordered organic semiconductors

While it is commonly accepted that the activation energy of the thermally activated polaron hopping transport in disordered organic semiconductors can be decoupled into a disorder and a polaron contribution, their relative weight is still controversial. This feature is quantified in terms of the so-called $C$ factor in the expression for the effective polaron mobility: ${\ensuremath{\mu}}_{e}\ensuremath{\propto}\mathrm{exp}[\ensuremath{-}{E}_{a}/{k}_{B}T\ensuremath{-}C{(\ensuremath{\sigma}/{k}_{B}T)}^{2}]$, where ${E}_{a}$ and $\ensuremath{\sigma}$ are the polaron activation energy and the energy width of a Gaussian density of states (DOS), respectively. A key issue is whether the universal scaling relation (implying a constant $C$ factor) regarding the polaron formation energy is really obeyed, as recently claimed in the literature [Seki and Wojcik, J. Chem. Phys. 145, 034106 (2016)]. In the present work, we reinvestigate this issue on the basis of the Marcus transition rate model using extensive kinetic Monte Carlo simulations as a benchmark tool. We compare the polaron-transport simulation data with results of analytical calculations by the effective medium approximation and multiple trapping and release approaches. The key result of this study is that the $C$ factor for Marcus polaron hopping depends on first the degree of carrier localization, i.e., the coupling between the sites, further whether quasiequilibrium has indeed been reached, and finally the $\ensuremath{\sigma}/{E}_{a}$ ratio. This implies that there is no universal scaling with respect to the relative contribution of polaron and disorder effect. Finally, we demonstrate that virtually the same values of the disorder parameter $\ensuremath{\sigma}$ are determined from available experimental data using the $C$ factors obtained here irrespective of whether the data are interpreted in terms of Marcus or Miller-Abrahams rates. This implies that molecular reorganization contributes only weakly to charge transport, and it justifies the use of the zero-order Miller-Abrahams rate model for evaluating the DOS width from temperature-dependent charge transport measurements regardless of whether or not polaron effects are accounted for.

Fabrication and temperature-dependent electrical characterization of a C-shape nanowire patterned by a DNA origami

We introduce a method based on directed molecular self-assembly to manufacture and electrically characterise C-shape gold nanowires which clearly deviate from typical linear shape due to the design of the template guiding the assembly. To this end, gold nanoparticles are arranged in the desired shape on a DNA-origami template and enhanced to form a continuous wire through electroless deposition. C-shape nanowires with a size below 150nm on a {hbox {SiO}_2}/hbox {Si} substrate are contacted with gold electrodes by means of electron beam lithography. Charge transport measurements of the nanowires show hopping, thermionic and tunneling transports at different temperatures in the 4.2K to 293K range. The different transport mechanisms indicate that the C-shape nanowires consist of metallic segments which are weakly coupled along the wires.

Oxygen vacancies in zirconium oxide as the blue luminescence centres and traps responsible for charge transport: Part II—Films

The origin of charge carrier traps in ZrO2 films was studied using charge transport measurements, EPR spectroscopy and quantum-chemical calculations. After the X-ray irradiation of the ZrO2 films, the EPR spectra from an interstitial oxygen and a negatively charged oxygen vacancy are observed. The trap thermal and optical activation energies 1.25 eV and 2.5 eV are estimated from the charge transport measurements. Within experiments on the extraction of minority carriers from silicon substrates, it was demonstrated that both electrons and holes can be trapped on oxygen vacancies in ZrO2. Hence, oxygen vacancies are supposed to operate as traps responsible for the charge transport in ZrO2 films.

100 °C-Langmuir–Blodgett Method for Fabricating Highly Oriented, Ultrathin Films of Polymeric Semiconductors

The Langmuir-Blodgett (LB) and Langmuir-Schaefer techniques facilitate thermodynamic favorability at an air-water interface, at which nanoscale molecular aggregations can be manipulated by micrometer- or millimeter-scale mechanics. The customary use of an aqueous subphase has limitations in the available temperature and spread materials. We present a general strategy to replace the aqueous subphase with an inert, low-vapor-pressure liquid, ethylene glycol. As a representative spread material that requires high-temperature processes, a semicrystalline polymeric semiconductor was investigated. We successfully demonstrated that the polymeric semiconductor spreads homogeneously across the entire surface of ethylene glycol heated to 100 °C using an LB trough, and spontaneously forms multilayers. Comprehensive studies such as X-ray diffraction, optical spectroscopy, and charge transport measurements revealed that barrier compression of solid-state polymer thin films during a high-temperature LB process produced uniaxial alignment of the polymer main chain with an averaged dichroic ratio of about 8, by which the electron transport concomitantly became highly anisotropic. The LB method presented in this work could be used to deposit thin films under ultimate environments, e.g., below 0 °C or above 100 °C, minimizing the effects of the vapor pressure of the subphase.

Hybrid Spintronic Materials from Conducting Polymers with Molecular Quantum Bits

AbstractHybrid materials consisting of organic semiconductors and molecular quantum bits promise to provide a novel platform for quantum spintronic applications. However, investigations of such materials, elucidating both the electrical and quantum dynamical properties of the same material have never been reported. Here the preparation of hybrid materials consisting of conducting polymers and molecular quantum bits is reported. Organic field‐effect transistor measurements demonstrate that the favorable electrical properties are preserved in the presence of the qubits. Chemical doping introduces charge carriers into the material, and variable‐temperature charge transport measurements reveal the existence of mobile charge carriers at temperatures as low as 15 K. Importantly, quantum coherence of the qubit is shown to be preserved up to temperatures of at least 30 K, that is, in the presence of mobile charge carriers. These results pave the way for employing such hybrid materials in novel molecular quantum spintronic architectures.

Electrophysiology Measurements of Metal Transport by MntH2 from Enterococcus faecalis.

Transition metals are essential trace elements and their high-affinity uptake is required for many organisms. Metal transporters are often characterised using metal-sensitive fluorescent dyes, limiting the metals and experimental conditions that can be studied. Here, we have tested whether metal transport by Enterococcus faecalis MntH2 can be measured with an electrophysiology method that is based on the solid-supported membrane technology. E. faecalis MntH2 belongs to the Natural Resistance-Associated Macrophage Protein (Nramp) family of proton-coupled transporters, which transport divalent transition metals and do not transport the earth metals. Electrophysiology confirms transport of Mn(II), Co(II), Zn(II) and Cd(II) by MntH2. However, no uptake responses for Cu(II), Fe(II) and Ni(II) were observed, while the presence of these metals abolishes the uptake signals for Mn(II). Fluorescence assays confirm that Ni(II) is transported. The data are discussed with respect to properties and structures of Nramp-type family members and the ability of electrophysiology to measure charge transport and not directly substrate transport.

Understanding Charge Transport in High‐Mobility p‐Doped Multicomponent Blend Organic Transistors

AbstractThe use of ternary systems comprising polymers, small molecules, and molecular dopants represents a promising approach for the development of high‐mobility, solution‐processed organic transistors. However, the current understanding of the charge transport in these complex systems, and particularly the role of molecular doping, is rather limited. Here, the role of the individual components in enhancing hole transport in the best‐performing ternary blend systems comprising the small molecule 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C8‐BTBT), the conjugated polymer indacenodithiophene‐alt‐benzothiadiazole (C16IDT‐BT), and the molecular p‐type dopant (C60F48) is investigated. Temperature‐dependent charge transport measurements reveal different charge transport regimes depending on the blend composition, crossing from a thermally activated to a band‐like behavior. Using the charge‐modulation spectroscopy technique, it is shown that in the case of the pristine blend, holes relax onto the conjugated polymer phase where shallow traps dominate carrier transport. Addition of a small amount of C60F48 deactivates those shallow traps allowing for a higher degree of hole delocalization within the highly crystalline C8‐BTBT domains located on the upper surface of the blend film. Such synergistic effect of a highly ordered C8‐BTBT phase, a polymer bridging grain boundaries, and p‐doping results in the exceptionally high hole mobilities and band‐like transport observed in this blend system.

Influence of the Accumulation Layer on the Spectral Properties of Full-Shell Majorana Nanowires

We study the influence of the accumulation layer on the spectral properties of semiconducting nanowires fully covered by a superconducting shell within the framework of the Bogoliubov–de Gennes equations. It is shown that both the decrease in the thickness of the layer and the increase in the ratio of the Fermi velocities in the shell and the core result in the enhancement of the spectral gap and restrict the parameter range corresponding to the topologically nontrivial phase. The presence of the accumulation layer can also lead to reentrant magnetic flux dependencies of the gap, which can be experimentally observed in measurements of charge transport through the nanowire in the Coulomb blockade conditions.

Backbone charge transport in double-stranded DNA.

Understanding charge transport in DNA molecules is a long-standing problem of fundamental importance across disciplines1,2. It is also of great technological interest due to DNA's ability to form versatile and complex programmable structures. Charge transport in DNA-based junctions has been reported using a wide variety of set-ups2-4, but experiments so far have yielded seemingly contradictory results that range from insulating5-8 or semiconducting9,10 to metallic-like behaviour11. As a result, the intrinsic charge transport mechanism in molecular junction set-ups is not well understood, which is mainly due to the lack of techniques to form reproducible and stable contacts with individual long DNA molecules. Here we report charge-transport measurements through single 30-nm-long double-stranded DNA (dsDNA) molecules with an experimental set-up that enables us to address individual molecules repeatedly and to measure the current-voltage characteristics from 5 K up to room temperature. Strikingly, we observed very high currents of tens of nanoamperes, which flowed through both homogeneous and non-homogeneous base-pair sequences. The currents are fairly temperature independent in the range 5-60 K and show a power-law decrease with temperature above 60 K, which is reminiscent of charge transport in organic crystals. Moreover, we show that the presence of even a single discontinuity ('nick') in both strands that compose the dsDNA leads to complete suppression of the current, which suggests that the backbones mediate the long-distance conduction in dsDNA, contrary to the common wisdom in DNA electronics2-4.

Charge transport measurements in compressed bulk graphene oxide

Abstract Charge transport measurements in compressed bulk graphene oxide (GO) have been studied within the temperature range 15-450 K. Structural properties and surface morphologies of the bulk compressed GO were studied using X-ray diffraction and transmission electron microscopy. Raman and X-ray photoelectron spectroscopies were also used to confirm the presence of graphitic phases and the various functional groups in the GO, respectively. Current-voltage characteristics of the GO measured with gold (Au) electrodes at different temperatures showed no Schottky barrier at the Au/GO interface. At low temperatures and low bias voltages, the electron transport through the compressed GO sample showed no significant voltage dependence, which is consistent with a direct tunneling mechanism at all the bias voltages (0.01 -1.0 V). It was also observed that no Fowler- Nordheim transport mechanism occurred within this bias voltage range.

Excitonic Laughlin states in ideal topological insulator flat bands and their possible presence in moiré superlattice materials

We investigate few- and many-body states in half-filled maximally symmetric topological insulator flat bands realized by two degenerate Landau levels which experience opposite magnetic fields. This serves as a toy model of flat bands in moir\'e materials in which valleys have Chern numbers $C= \pm 1$. We argue that although the spontaneously polarized Ising Chern magnet is a natural ground state for repulsive Coulomb interactions, it can be in reasonable energetic competition with correlated states which can be viewed as Laughlin states of excitons when short distance corrections to the interaction are included. This is because charge neutral excitons in these bands behave effectively as charged particles in ordinary Landau levels. In particular, the Ising Chern magnet is no longer the ground state once the strength of a short range intra-valley repulsion is about $30\%$ larger than the inter-valley repulsion. Remarkably, these excitonic Laughlin states feature valley number fractionalization but no charge fractionalization and a quantized charge Hall conductivity identical to the Ising magnet, $\sigma_{xy}= \pm e^2/h$, and thus cannot be distinguished from it by ordinary charge transport measurements. The most compact excitonic Laughlin state that can be constructed in these bands is an analogue of $\nu=1/4$ bosonic Laughlin state and has no valley polarization even though it spontaneously breaks time reversal symmetry with a charge Hall conductivity $\sigma_{xy}= \pm e^2/h$.

Charge transport measurements in compressed bulk graphene oxide

Abstract Charge transport measurements in compressed bulk graphene oxide (GO) have been studied within the temperature range 15-450 K. Structural properties and surface morphologies of the bulk compressed GO were studied using X-ray diffraction and transmission electron microscopy. Raman and X-ray photoelectron spectroscopies were also used to confirm the presence of graphitic phases and the various functional groups in the GO, respectively. Current-voltage characteristics of the GO measured with gold (Au) electrodes at different temperatures showed no Schottky barrier at the Au/GO interface. At low temperatures and low bias voltages, the electron transport through the compressed GO sample showed no significant voltage dependence, which is consistent with a direct tunneling mechanism at all the bias voltages (0.01 -1.0 V). It was also observed that no Fowler- Nordheim transport mechanism occurred within this bias voltage range.