arXiv subjects

Mark C. Hersam

Publications and source records attributed to Mark C. Hersam.

At least 55 records · Page 3Linked to original sources

arXiv2020

Nanoscale probing of image-potential states and electron transfer doping in borophene polymorphs

Using field-emission resonance spectroscopy with an ultrahigh vacuum scanning tunneling microscope, we reveal Stark-shifted image-potential states of the v_1/6 and v_1/5 borophene polymorphs on Ag(111) with long lifetimes, suggesting high borophene lattice and interface quality. These image-potential states allow the local work function and interfacial charge transfer of borophene to be probed at the nanoscale and test the widely employed self-doping model of borophene. Supported by apparent barrier height measurements and density functional theory calculations, electron transfer doping occurs for both borophene phases from the Ag(111) substrate. In contradiction with the self-doping model, a higher electron transfer doping level occurs for denser v_1/6 borophene compared to v_1/5 borophene, thus revealing the importance of substrate effects on borophene electron transfer.

cond-mat.mtrl-sci↗

arXiv2019

Hot Carrier and Surface Recombination Dynamics in Layered InSe Crystals

Layered indium selenide (InSe) is a van der Waals solid that has emerged as a promising material for high-performance ultrathin solar cells. The optoelectronic parameters that are critical to photoconversion efficiencies, such as hot carrier lifetime and surface recombination velocity, are however largely unexplored in InSe. Here, these key photophysical properties of layered InSe are measured with femtosecond transient reflection spectroscopy. The hot carrier cooling process is found to occur through phonon scattering. The surface recombination velocity and ambipolar diffusion coefficient are extracted from fits to the pump energy-dependent transient reflection kinetics using a free carrier diffusion model. The extracted surface recombination velocity is approximately an order of magnitude larger than that for methylammonium lead-iodide perovskites, suggesting that surface recombination is a principal source of photocarrier loss in InSe. The extracted ambipolar diffusion coefficient is consistent with previously reported values of InSe carrier mobility.

cond-mat.mtrl-sci↗

arXiv2019

Low Frequency Carrier Kinetics in Perovskite Solar Cells

Hybrid organic-inorganic halide perovskite solar cells have emerged as leading candidates for third-generation photovoltaic technology. Despite the rapid improvement in power conversion efficiency (PCE) for perovskite solar cells in recent years, the low-frequency carrier kinetics that underlie practical roadblocks such as hysteresis and degradation remain relatively poorly understood. In an effort to bridge this knowledge gap, we perform here correlated low-frequency noise (LFN) and impedance spectroscopy (IS) characterization that elucidates carrier kinetics in operating perovskite solar cells. Specifically, we focus on planar cell geometries with a SnO2 electron transport layer and two different hole transport layers, namely, poly(triarylamine) (PTAA) and Spiro-OMeTAD. PTAA and Sprio-OMeTAD cells with moderate PCEs of 5 to 12 percent possess a Lorentzian feature at 200 Hz in LFN measurements that corresponds to a crossover from electrode to dielectric polarization. In comparison, Spiro-OMeTAD cells with high PCEs (15 percent) show four orders of magnitude lower LFN amplitude and are accompanied by a cyclostationary process. Through a systematic study of more than a dozen solar cells, we establish a correlation with noise amplitude, power conversion efficiency, and fill factor. Overall, this work establishes correlated LFN and IS as an effective methodology for quantifying low frequency carrier kinetics in perovskite solar cells, thereby providing new physical insights that can rationally guide ongoing efforts to improve device performance, reproducibility, and stability.

physics.app-ph↗

arXiv2018

Self-Assembled Photochromic Molecular Dipoles for High Performance Polymer Thin-Film Transistors

The development of high-performance multifunctional polymer-based electronic circuits is a major step towards future flexible electronics. Here, we demonstrate a tunable approach to fabricate such devices based on rationally designed dielectric super-lattice structures with photochromic azo-benzene molecules. These nanodielectrics possessing ionic, molecular, and atomic polarization are utilized in polymer thin-film transistors (TFTs) to realize high performance electronics with p-type field-effect mobility exceeding 2 cm^2/(V.s). A crossover in the transport mechanism from electrostatic dipolar disorder to ionic-induced disorder is observed in the transistor characteristics over a range of temperatures. The facile supramolecular design allows the possibility to optically control the extent of molecular and ionic polarization in the ultra-thin nanodielectric. Thus, we demonstrate a three-fold increase in the capacitance from 0.1 uF/cm^2 to 0.34 uF/cm^2, which results in a 200% increase in TFT channel current.

physics.app-ph↗

arXiv2018

Mechanisms of Ultrafast Charge Separation in a PTB7/Monolayer MoS2 van der Waals Heterojunction

Mixed-dimensional van der Waals heterojunctions comprising polymer and twodimensional (2D) semiconductors have many characteristics of an ideal charge separation interface for optoelectronic and photonic applications. However, the photoelectron dynamics at polymer- 2D semiconductor heterojunction interfaces are currently not sufficiently understood to guide the optimization of devices for these applications. This manuscript is a report of a systematic exploration of the time-dependent photophysical processes that occur upon photoexcitation of a type-II heterojunction between the polymer PTB7 and monolayer MoS2. In particular, photoinduced electron transfer from PTB7 to electronically hot states of MoS2 occurs in less than 250 fs. This process is followed by a slower (1-5 ps) exciton diffusion-limited electron transfer from PTB7 to MoS2 with a yield of 58%, and a sub-3-ps photoinduced hole transfer from MoS2 to PTB7. The equilibrium between excitons and polaron pairs in PTB7 determines the charge separation yield, whereas the 3-4 ns lifetime of photogenerated carriers is limited by MoS2 defects. Overall, this work elucidates the mechanisms of ultrafast charge carrier dynamics at PTB7-MoS2 interfaces, which will inform ongoing efforts to exploit polymer-2D semiconductor heterojunctions for photovoltaic and photodetector applications.

cond-mat.mtrl-sci↗

arXiv2018

Charge Separation at Mixed-Dimensional Single and Multilayer MoS2/Silicon Nanowire Heterojunctions

Layered two-dimensional (2-D) semiconductors can be combined with other low-dimensional semiconductors to form non-planar mixed-dimensional van der Waals (vdW) heterojunctions whose charge transport behavior is influenced by the heterojunction geometry, providing a new degree of freedom to engineer device functions. Towards that end, we investigated the photoresponse of Si nanowire/MoS2 heterojunction diodes with scanning photocurrent microscopy and time-resolved photocurrent measurements. Comparison of n-Si/MoS2 isotype heterojunctions with p-Si/MoS2 heterojunction diodes under varying biases shows that the depletion region in the p-n heterojunction promotes exciton dissociation and carrier collection. We measure an instrument limited response time of 1 us, which is 10 times faster than previously reported response times for planar Si/MoS2 devices, highlighting the advantages of the 1-D/2-D heterojunction. Finite element simulations of device models provide a detailed understanding of how the electrostatics affect charge transport in nanowire/vdW heterojunctions and inform the design of future vdW heterojunction photodetectors and transistors.

physics.app-ph↗

arXiv2018

Gate-tunable memristors from monolayer MoS2

We report here gate-tunable memristors based on monolayer MoS2 grown by chemical vapor deposition (CVD). These memristors are fabricated in a field-effect geometry with the channel consisting of polycrystalline MoS2 films with grain sizes of 3-5 um. The device characteristics show switching ratios up to 500, with the resistance in individual states being continuously gate-tunable by over three orders of magnitude. The resistive switching results from dynamically varying threshold voltage and Schottky barrier heights, whose underlying physical mechanism appears to be vacancy migration and/or charge trapping. Top-gated devices achieve reversible tuning of the threshold voltage, with potential utility in non-volatile memory or neuromorphic architectures.

physics.app-ph↗

arXiv2018

Multi-Terminal Memtransistors from Polycrystalline Monolayer MoS2

In the last decade, a 2-terminal passive circuit element called a memristor has been developed for non-volatile resistive random access memory and has more recently shown promise for neuromorphic computing. Compared to flash memory, memristors have higher endurance, multi-bit data storage, and faster read/write times. However, although 2-terminal memristors have demonstrated basic neural functions, synapses in the human brain outnumber neurons by more than a factor of 1000, which implies that multiterminal memristors are needed to perform complex functions such as heterosynaptic plasticity. Previous attempts to move beyond 2-terminal memristors include the 3-terminal Widrow-Hoff memistor and field-effect transistors with nanoionic gates or floating gates, albeit without memristive switching in the transistor. Here, we report the scalable experimental realization of a multi-terminal hybrid memristor and transistor (i.e., memtransistor) using polycrystalline monolayer MoS2. Two-dimensional (2D) MoS2 memtransistors show gate tunability in individual states by 4 orders of magnitude in addition to large switching ratios with high cycling endurance and long-term retention of states. In addition to conventional neural learning behavior of long-term potentiation/depression, 6-terminal MoS2 memtransistors possess gate-tunable heterosynaptic functionality that is not achievable using 2-terminal memristors. For example, the conductance between a pair of two floating electrodes (pre-synaptic and post-synaptic neurons) is varied by 10X by applying voltage pulses to modulatory terminals. In situ scanning probe microscopy, cryogenic charge transport measurements, and device modeling reveal that bias-induced MoS2 defect motion drives resistive switching by dynamically varying Schottky barrier heights.

cond-mat.mtrl-sci↗

arXiv2018

Graphene-enabled, directed nanomaterial placement from solution for large-scale device integration

Controlled placement of nanomaterials at predefined locations with nanoscale precision remains among the most challenging problems that inhibit their large-scale integration in the field of semiconductor process technology. Methods based on surface functionalization have a drawback where undesired chemical modifications can occur and deteriorate the deposited material. The application of electric-field assisted placement techniques eliminates the element of chemical treatment; however, it requires an incorporation of conductive placement electrodes that limit the performance, scaling, and density of integrated electronic devices. Here, we report a method for electric-field assisted placement of solution-processed nanomaterials by using large-scale graphene layers featuring nanoscale deposition sites. The structured graphene layers are prepared via either transfer or synthesis on standard substrates, then are removed without residue once nanomaterial deposition is completed, yielding material assemblies with nanoscale resolution that cover surface areas larger than 1mm2. In order to demonstrate the broad applicability, we have assembled representative zero-, one-, and two-dimensional semiconductors at predefined substrate locations and integrated them into nanoelectronic devices. This graphene-based placement technique affords nanoscale resolution at wafer scale, and could enable mass manufacturing of nanoelectronics and optoelectronics involving a wide range of nanomaterials prepared via solution-based approaches.

physics.app-ph↗

arXiv2018

Self-Aligned van der Waals Heterojunction Diodes and Transistors

A general self-aligned fabrication scheme is reported here for a diverse class of electronic devices based on van der Waals materials and heterojunctions. In particular, self-alignment enables the fabrication of source-gated transistors in monolayer MoS2 with near-ideal current saturation characteristics and channel lengths down to 135 nm. Furthermore, self-alignment of van der Waals p-n heterojunction diodes achieves complete electrostatic control of both the p-type and n-type constituent semiconductors in a dual-gated geometry, resulting in gate-tunable mean and variance of anti-ambipolar Gaussian characteristics. Through finite-element device simulations, the operating principles of source-gated transistors and dual-gated anti-ambipolar devices are elucidated, thus providing design rules for additional devices that employ self-aligned geometries. For example, the versatility of this scheme is demonstrated via contact-doped MoS2 homojunction diodes and mixed-dimensional heterojunctions based on organic semiconductors. The scalability of this approach is also shown by fabricating self-aligned short-channel transistors with sub-diffraction channel lengths in the range of 150 nm to 800 nm using photolithography on large-area MoS2 films grown by chemical vapor deposition. Overall, this self-aligned fabrication method represents an important step towards the scalable integration of van der Waals heterojunction devices into more sophisticated circuits and systems.

physics.app-ph↗

arXiv2018

Electronic Transport in Two-Dimensional Materials

Two-dimensional (2D) materials have captured the attention of the scientific community due to the wide range of unique properties at nanometer-scale thicknesses. While significant exploratory research in 2D materials has been achieved, the understanding of 2D electronic transport and carrier dynamics remains in a nascent stage. Furthermore, since prior review articles have provided general overviews of 2D materials or specifically focused on charge transport in graphene, here we instead highlight charge transport mechanisms in post-graphene 2D materials with particular emphasis on transition metal dichalcogenides and black phosphorus. For these systems, we delineate the intricacies of electronic transport including bandstructure control with thickness and external fields, valley polarization, scattering mechanisms, electrical contacts, and doping. In addition, electronic interactions between 2D materials are considered in the form of van der Waals heterojunctions and composite films. This review concludes with a perspective on the most promising future directions in this fast-evolving field.

cond-mat.mtrl-sci↗

arXiv2017

Valley-selective optical Stark effect probed by Kerr rotation

The ability to monitor and control distinct states is at the heart of emerging quantum technologies. The valley pseudospin in transition metal dichalcogenide (TMDC) monolayers is a promising degree of freedom for such control, with the optical Stark effect allowing for valley-selective manipulation of energy levels in WS$_2$ and WSe$_2$ using ultrafast optical pulses. Despite these advances, understanding of valley-sensitive optical Stark shifts in TMDCs has been limited by reflectance-based detection methods where the signal is small and prone to background effects. More sensitive polarization-based spectroscopy is required to better probe ultrafast Stark shifts for all-optical manipulation of valley energy levels. Here, we show time-resolved Kerr rotation to be a more sensitive probe of the valley-selective optical Stark effect in monolayer TMDCs. Compared to the established time-resolved reflectance methods, Kerr rotation is less sensitive to background effects. Kerr rotation provides a five-fold improvement in the signal-to-noise ratio of the Stark effect optical signal and a more precise estimate of the energy shift. This increased sensitivity allows for observation of an optical Stark shift in monolayer MoS$_2$ that exhibits both valley- and energy-selectivity, demonstrating the promise of this method for investigating this effect in other layered materials and heterostructures.

cond-mat.mtrl-sci↗

arXiv2017

Correlated In-Situ Low-Frequency Noise and Impedance Spectroscopy Reveal Recombination Dynamics in Organic Solar Cells using Fullerene and Non-Fullerene Acceptors

Non-fullerene acceptors based on perylenediimides (PDIs) have garnered significant interest as an alternative to fullerene acceptors in organic photovoltaics (OPVs), but their charge transport phenomena are not well understood, especially in bulk heterojunctions (BHJs). Here, we investigate charge transport and current fluctuations by performing correlated low-frequency noise and impedance spectroscopy measurements on two BHJ OPV systems, one employing a fullerene acceptor and the other employing a dimeric PDI acceptor. In the dark, these measurements reveal that PDI-based OPVs have a greater degree of recombination in comparison to fullerene-based OPVs. Furthermore, for the first time in organic solar cells, 1/f noise data are fit to the Kleinpenning model to reveal underlying current fluctuations in different transport regimes. Under illumination, 1/f noise increases by approximately four orders of magnitude for the fullerene-based OPVs and three orders of magnitude for the PDI-based OPVs. An inverse correlation is also observed between noise spectral density and power conversion efficiency. Overall, these results show that low-frequency noise spectroscopy is an effective in-situ diagnostic tool to assess charge transport in emerging photovoltaic materials, thereby providing quantitative guidance for the design of next-generation solar cell materials and technologies.

physics.app-ph↗

arXiv2017

Control of interlayer delocalization in 2H transition metal dichalcogenides

It is assessed in detail both experimentally and theoretically how the interlayer coupling of transition metal dichalcogenides controls the electronic properties of the respective devices. Gated transition metal dichalcogenide structures show electrons and holes to either localize in individual monolayers, or delocalize beyond multiple layers - depending on the balance between spin-orbit inter- action and interlayer hopping. This balance depends on layer thickness, momentum space symmetry points and applied gate fields. A good quantitative agreement of predictions and measurements of the quantum confined Stark effect in gated MoS2 systems unveils intralayer excitons as major source for the observed photoluminesence.

cond-mat.mes-hall↗

arXiv2017

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene MoS2 van der Waals Heterojunction

Van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed dimensional p-n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS2 (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene-MoS2 p-n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS2 excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS2 decay processes, the hole transfer yield from MoS2 to pentacene is found to be approximately 50 percent, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene-MoS2 p-n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies.

cond-mat.mes-hall↗

arXiv2016

Mutual Photoluminescence Quenching and Photovoltaic Effect in Large-Area Single-Layer MoS2-Polymer Heterojunctions

Two-dimensional transition metal dichalcogenides (TMDCs) have recently attracted attention due to their superlative optical and electronic properties. In particular, their extraordinary optical absorption and semiconducting band gap have enabled demonstrations of photovoltaic response from heterostructures composed of TMDCs and other organic or inorganic materials. However, these early studies were limited to devices at the micrometer scale and/or failed to exploit the unique optical absorption properties of single-layer TMDCs. Here we present an experimental realization of a large-area type-II photovoltaic heterojunction using single-layer molybdenum disulfide (MoS2) as the primary absorber, by coupling it to the organic π-donor polymer PTB7. This TMDC-polymer heterojunction exhibits photoluminescence intensity that is tunable as a function of the thickness of the polymer layer, ultimately enabling complete quenching of the TMDC photoluminescence. The strong optical absorption in the TMDC-polymer heterojunction produces an internal quantum efficiency exceeding 40% for an overall cell thickness of less than 20 nm, resulting in exceptional current density per absorbing thickness in comparison to other organic and inorganic solar cells. Furthermore, this work provides new insight into the recombination processes in type-II TMDC-polymer heterojunctions and thus provides quantitative guidance to ongoing efforts to realize efficient TMDC-based solar cells.

cond-mat.mtrl-sci↗

arXiv2016

Mixed-Dimensional van der Waals Heterostructures

The isolation of a growing number of two-dimensional (2D) materials has inspired worldwide efforts to integrate distinct 2D materials into van der Waals (vdW) heterostructures. Given that any passivated, dangling bond-free surface will interact with another via vdW forces, the vdW heterostructure concept can be extended to include the integration of 2D materials with non-2D materials that adhere primarily through noncovalent interactions. In this review, we present a succinct and critical survey of emerging mixed-dimensional (2D + nD, where n is 0, 1 or 3) heterostructure devices. By comparing and contrasting with all-2D vdW heterostructures as well as with competing conventional technologies, the challenges and opportunities for mixed-dimensional vdW heterostructures are highlighted.

cond-mat.mtrl-sci↗

arXiv2016

Covalent Functionalization and Passivation of Exfoliated Black Phosphorus via Aryl Diazonium Chemistry

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical, and electronic properties. Exfoliated black phosphorus, a layered two-dimensional semiconductor exhibiting favorable charge carrier mobility, tunable bandgap, and highly anisotropic properties, is chemically reactive and degrades rapidly in ambient conditions. In contrast, here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated black phosphorus even following weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent, and alters the electronic properties of exfoliated black phosphorus, ultimately yielding a strong, tunable p-type doping that simultaneously improves field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated black phosphorus, thus improving its prospects for nanoelectronic applications.

cond-mat.mtrl-sci↗