arXiv subjects

Tobin J. Marks

Publications and source records attributed to Tobin J. Marks.

At least 19 recordsLinked to original sources

arXiv2025

Modifying the Optical Emission of Vanadyl Phthalocyanine via Molecular Self-Assembly on van der Waals Materials

Vanadyl phthalocyanine (VOPc) is a promising organic molecule for applications in quantum information because of its thermal stability, efficient processing, and potential as a spin qubit. The deposition of VOPc in different molecular orientations allows the properties to be customized for integration into various devices. However, such customization has yet to be fully leveraged to alter its intrinsic properties, particularly optical emission. Normally, VOPc films on dielectric substrates emit a broad photoluminescence peak in the near-infrared range, attributed to transitions in the Pc ring from its pi orbital structure. In this work, we demonstrate that the dominant optical transition of VOPc can be shifted by over 250 meV through the controlled deposition of thin films on van der Waals material substrates. The weak interactions with van der Waals materials allow the molecules to uniquely self-assemble, resulting in modified optical behavior modulated by molecular phase and thickness. This work connects the self-assembling properties of molecules with their altered electronic structures and the resulting optical emission.

cond-mat.mtrl-sci↗

arXiv2025

High Temperature Quantum Emission from Covalently Functionalized van der Waals Heterostructures

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are attractive nanomaterials for quantum information applications due to single photon emission (SPE) from atomic defects, primarily tungsten diselenide (WSe2) monolayers. Defect and strain engineering techniques have been developed to yield high purity, deterministically positioned SPE in WSe2. However, a major challenge in application of these techniques is the low temperature required to observe defect-bound TMD exciton emission, typically limiting SPE to T<30 K. SPE at higher temperatures either loses purity or requires integration into complex devices such as optical cavities. Here, 2D heterostructure engineering and molecular functionalization are combined to achieve high purity (>90%) SPE in strained WSe2 persisting to over T=90 K. Covalent diazonium functionalization of graphite in a layered WSe2/graphite heterostructure maintains high purity up to T=90 K and single-photon source integrity up to T=115 K. This method preserves the best qualities of SPE from WSe2 while increasing working temperature to more than three times the typical range. This work demonstrates the versatility of surface functionalization and heterostructure design to synergistically improve the properties of quantum emission and offers new insights into the phenomenon of SPE from 2D materials.

cond-mat.mtrl-sci↗

arXiv2024

The Role of Defect Geometry in Localized Emission from Monolayer Tungsten Dichalcogenides

Understanding the mechanism of single photon emission (SPE) in two-dimensional (2D) material is an unsolved problem important for quantum optical materials and the development of quantum information applications. In 2D transition metal dichalcogenides (TMDs) such as tungsten diselenide (WSe2), quantum emission has been broadly attributed to exciton localization from atomic point defects, yet the precise microscopic origins are not fully understood. This work introduces an empirically grounded computational framework that explains both the origins of facile SPE in WSe2 and its relative scarcity in related TMD, tungsten disulfide. High resolution microscopy identifies native defect geometries existing in monolayer WSe2 lattices providing the ingredients necessary to build a realistic model. The qualitative effects of chalcogen type, defect geometry, and mechanical strain on the electronic structure are then individually assessed using density functional theory, from which a specific divacancy configuration emerges as the candidate for localized single-electron transitions that match observed spectral energies. Spectroscopy and photon correlation measurements further validate this model, establishing a self-consistent link between defect geometry, electronic structure, and quantum emission. By isolating the distinct roles of chalcogen type, defect configuration, and mechanical strain, this work provides a thorough investigation of exciton localization and optical behavior, contributing to a clearer picture of the physical drivers of single photon emission in tungsten-based TMDs.

cond-mat.mtrl-sci↗

arXiv2021

Range-Separated Hybrid Functionals for Mixed-Dimensional Heterojunctions: Application to Phthalocyanines/MoS2

We analyze the electronic structure and level alignment of transition-metal phthalocyanine (MPc) molecules adsorbed on two-dimensional MoS$_2$ employing density functional theory (DFT) calculations. We develop a procedure for multi-objective optimal tuning of parameters of range-separated hybrid functionals in these mixed-dimensional systems. Using this procedure, which leads to the asymptotically-correct exchange-correlation potential between molecule and two-dimensional material, we obtain electronic structures consistent with experimental photoemission results for both energy level alignment and electronic bandgaps, representing a significant advance compared to standard DFT methods. We elucidate the MoS$_2$ valence resonance with the transition-metal phthalocyanine non-frontier 3$d$ orbitals and its dependence on the transition metal atomic number. Based on our calculations, we derive parameter-free, model self-energy corrections that quantitatively accounts for the effects of the heterogeneous dielectric environment on the electronic structure of these mixed-dimensional heterojunctions.

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↗

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↗

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↗

arXiv2016

Probing Out-of-Plane Charge Transport in Black Phosphorus with Graphene-Contacted Vertical Field-Effect Transistors

Black phosphorus (BP) has recently emerged as a promising narrow band gap layered semiconductor with optoelectronic properties that bridge the gap between semi-metallic graphene and wide band gap transition metal dichalcogenides such as MoS2. To date, BP field-effect transistors have utilized a lateral geometry with in-plane transport dominating device characteristics. In contrast, we present here a vertical field-effect transistor geometry based on a graphene/BP van der Waals heterostructure. The resulting device characteristics include high on-state current densities (> 1600 A/cm2) and current on/off ratios exceeding 800 at low temperature. Two distinct charge transport mechanisms are identified, which are dominant for different regimes of temperature and gate voltage. In particular, the Schottky barrier between graphene and BP determines charge transport at high temperatures and positive gate voltages, whereas tunneling dominates at low temperatures and negative gate voltages. These results elucidate out-of-plane electronic transport in BP, and thus have implications for the design and operation of BP-based van der Waals heterostructures.

cond-mat.mtrl-sci↗

arXiv2015

Hybrid, Gate-Tunable, van der Waals p-n Heterojunctions from Pentacene and MoS2

The recent emergence of a wide variety of two-dimensional (2D) materials has created new opportunities for device concepts and applications. In particular, the availability of semiconducting transition metal dichalcogenides, in addition to semi-metallic graphene and insulating boron nitride, has enabled the fabrication of all 2D van der Waals heterostructure devices. Furthermore, the concept of van der Waals heterostructures has the potential to be significantly broadened beyond layered solids. For example, molecular and polymeric organic solids, whose surface atoms possess saturated bonds, are also known to interact via van der Waals forces and thus offer an alternative for scalable integration with 2D materials. Here, we demonstrate the integration of an organic small molecule p-type semiconductor, pentacene, with a 2D n-type semiconductor, MoS2. The resulting p-n heterojunction is gate-tunable and shows asymmetric control over the anti-ambipolar transfer characteristic. In addition, the pentacene-MoS2 heterojunction exhibits a photovoltaic effect attributable to type II band alignment, which suggests that MoS2 can function as an acceptor in hybrid solar cells.

cond-mat.mtrl-sci↗

arXiv2015

Investigation of Band-Offsets at Monolayer-Multilayer MoS2 Junctions by Scanning Photocurrent Microscopy

The thickness-dependent band structure of MoS2 implies that discontinuities in energy bands exist at the interface of monolayer (1L) and multilayer (ML) thin films. The characteristics of such heterojunctions are analyzed here using current versus voltage measurements, scanning photocurrent microscopy, and finite element simulations of charge carrier transport. Rectifying I-V curves are consistently observed between contacts on opposite sides of 1L-ML junctions, and a strong bias-dependent photocurrent is observed at the junction. Finite element device simulations with varying carrier concentrations and electron affinities show that a type II band alignment at single layer/multi-layer junctions reproduces both the rectifying electrical characteristics and the photocurrent response under bias. However, the zero-bias junction photocurrent and its energy dependence are not explained by conventional photovoltaic and photothermoelectric mechanisms, indicating the contributions of hot carriers.

cond-mat.mes-hall↗

arXiv2014

Large-area, low-voltage, anti-ambipolar heterojunctions from solution-processed semiconductors

The emergence of semiconducting materials with inert or dangling bond-free surfaces has created opportunities to form van der Waals heterostructures without the constraints of traditional epitaxial growth. For example, layered two-dimensional (2D) semiconductors have been incorporated into heterostructure devices with gate-tunable electronic and optical functionalities. However, 2D materials present processing challenges that have prevented these heterostructures from being produced with sufficient scalability and/or homogeneity to enable their incorporation into large-area integrated circuits. Here, we extend the concept of van der Waals heterojunctions to semiconducting p-type single-walled carbon nanotube (s-SWCNT) and n-type amorphous indium gallium zinc oxide (a-IGZO) thin films that can be solution-processed or sputtered with high spatial uniformity at the wafer scale. The resulting large-area, low-voltage p-n heterojunctions exhibit anti-ambipolar transfer characteristics with high on/off ratios that are well-suited for electronic, optoelectronic, and telecommunication technologies.

cond-mat.mtrl-sci↗

arXiv2014

Effective Passivation of Exfoliated Black Phosphorus Transistors against Ambient Degradation

Unencapsulated, exfoliated black phosphorus (BP) flakes are found to chemically degrade upon exposure to ambient conditions. Atomic force microscopy, electrostatic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are employed to characterize the structure and chemistry of the degradation process, suggesting that O2 saturated H2O irreversibly reacts with BP to form oxidized phosphorus species. This interpretation is further supported by the observation that BP degradation occurs more rapidly on hydrophobic octadecyltrichlorosilane self-assembled monolayers and on H-Si(111), versus hydrophilic SiO2. For unencapsulated BP field-effect transistors, the ambient degradation causes large increases in threshold voltage after 6 hours in ambient, followed by a ~10^3 decrease in FET current on/off ratio and mobility after 48 hours. Atomic layer deposited AlOx overlayers effectively suppress ambient degradation, allowing encapsulated BP FETs to maintain high on/off ratios of ~10^3 and mobilities of ~100 cm2/(V*s) for over two weeks in ambient. This work shows that the ambient degradation of BP can be managed effectively when the flakes are sufficiently passivated. In turn, our strategy for enhancing BP environmental stability will accelerate efforts to implement BP in electronic and optoelectronic applications.

cond-mat.mes-hall↗

arXiv2014

Influence of Stoichiometry on the Optical and Electrical Properties of Chemical Vapor Deposition Derived MoS$_{2}$

Ultrathin transition metal dichalcogenides (TMDCs) of Mo and W show great potential for digital electronics and optoelectronic applications. Whereas early studies were limited to mechanically exfoliated flakes, the large-area synthesis of 2D TMDCs has now been realized by chemical vapor deposition (CVD) based on a sulfurization reaction. Since then, the optoelectronic properties of CVD grown monolayer MoS$_{2}$ have been heavily investigated, but the influence of stoichiometry on the electrical and optical properties has been largely overlooked. Here we systematically vary the stoichiometry of monolayer MoS$_{2}$ during CVD via controlled sulfurization and investigate the associated changes in photoluminescence and electrical properties. X-ray photoelectron spectroscopy is employed to measure relative variations in stoichiometry and the persistence of MoO$_{x}$ species. As MoS$_{2-δ}$ is reduced (increasing δ), the field-effect mobility of monolayer transistors increases while the photoluminescence yield becomes non-uniform. Devices fabricated from monolayers with the lowest sulfur content have negligible hysteresis and a threshold voltage of ~0 V. We conclude that the electrical and optical properties of monolayer MoS$_{2}$ crystals can be tuned via stoichiometry engineering to meet the requirements of various applications.

cond-mat.mtrl-sci↗

arXiv2014

Wafer-scale solution-derived molecular gate dielectrics for low-voltage graphene electronics

Graphene field-effect transistors are integrated with solution-processed multilayer hybrid organic-inorganic self-assembled nanodielectrics (SANDs). The resulting devices exhibit low-operating voltage (2 V), negligible hysteresis, current saturation with intrinsic gain > 1.0 in vacuum (pressure < 2 x 10-5 Torr), and overall improved performance compared to control devices on conventional SiO2 gate dielectrics. Statistical analysis of the field-effect mobility and residual carrier concentration demonstrate high spatial uniformity of the dielectric interfacial properties and graphene transistor characteristics over full 3 inch wafers. This work thus establishes SANDs as an effective platform for large-area, high-performance graphene electronics.

cond-mat.mtrl-sci↗

arXiv2014

Emerging Device Applications for Semiconducting Two-Dimensional Transition Metal Dichalcogenides

With advances in exfoliation and synthetic techniques, atomically thin films of semiconducting transition metal dichalcogenides have recently been isolated and characterized. Their two-dimensional structure, coupled with a direct band gap in the visible portion of the electromagnetic spectrum, suggests suitability for digital electronics and optoelectronics. Towards that end, several classes of high-performance devices have been reported along with significant progress in understanding their physical properties. Here, we present a review of the architecture, operating principles, and physics of electronic and optoelectronic devices based on ultrathin transition metal dichalcogenide semiconductors. By critically assessing and comparing the performance of these devices with competing technologies, the merits and shortcomings of this emerging class of electronic materials are identified, thereby providing a roadmap for future development.

cond-mat.mes-hall↗