Large and Tunable Photothermoelectric Effect in Single-Layer MoS₂

We study the photoresponse of single-layer MoS₂ field-effect transistors by scanning photocurrent microscopy. We find that, unlike in many other semiconductors, the photocurrent generation in single-layer MoS₂ is dominated by the photothermoelectric effect and not by the separation of photoexcited electron–hole pairs across the Schottky barriers at the MoS₂/electrode interfaces. We observe a large value for the Seebeck coefficient for single-layer MoS₂ that by an external electric field can be tuned between −4 × 10² and −1 × 10⁵ μV K^–1. This large and tunable Seebeck coefficient of the single-layer MoS₂ paves the way to new applications of this material such as on-chip thermopower generation and waste thermal energy harvesting

Fast and Broadband Photoresponse of Few-Layer Black Phosphorus Field-Effect Transistors

Few-layer black phosphorus, a new elemental two-dimensional (2D) material recently isolated by mechanical exfoliation, is a high-mobility layered semiconductor with a direct bandgap that is predicted to strongly depend on the number of layers, from 0.35 eV (bulk) to 2.0 eV (single layer). Therefore, black phosphorus is an appealing candidate for tunable photodetection from the visible to the infrared part of the spectrum. We study the photoresponse of field-effect transistors (FETs) made of few-layer black phosphorus (3–8 nm thick), as a function of excitation wavelength, power, and frequency. In the dark state, the black phosphorus FETs can be tuned both in hole and electron doping regimes allowing for ambipolar operation. We measure mobilities in the order of 100 cm²/V s and a current ON/OFF ratio larger than 10³. Upon illumination, the black phosphorus transistors show a response to excitation wavelengths from the visible region up to 940 nm and a rise time of about 1 ms, demonstrating broadband and fast detection. The responsivity reaches 4.8 mA/W, and it could be drastically enhanced by engineering a detector based on a PN junction. The ambipolar behavior coupled to the fast and broadband photodetection make few-layer black phosphorus a promising 2D material for photodetection across the visible and near-infrared part of the electromagnetic spectrum

Local Strain Engineering in Atomically Thin MoS₂

Controlling the bandstructure through local-strain engineering is an exciting avenue for tailoring optoelectronic properties of materials at the nanoscale. Atomically thin materials are particularly well-suited for this purpose because they can withstand extreme nonhomogeneous deformations before rupture. Here, we study the effect of large localized strain in the electronic bandstructure of atomically thin MoS₂. Using photoluminescence imaging, we observe a strain-induced reduction of the direct bandgap and funneling of photogenerated excitons toward regions of higher strain. To understand these results, we develop a nonuniform tight-binding model to calculate the electronic properties of MoS₂ nanolayers with complex and realistic local strain geometries, finding good agreement with our experimental results

Photovoltaic and Photothermoelectric Effect in a Double-Gated WSe₂ Device

Tungsten diselenide (WSe₂), a semiconducting transition metal dichalcogenide (TMDC), shows great potential as active material in optoelectronic devices due to its ambipolarity and direct bandgap in its single-layer form. Recently, different groups have exploited the ambipolarity of WSe₂ to realize electrically tunable PN junctions, demonstrating its potential for digital electronics and solar cell applications. In this Letter, we focus on the different photocurrent generation mechanisms in a double-gated WSe₂ device by measuring the photocurrent (and photovoltage) as the local gate voltages are varied independently in combination with above- and below-bandgap illumination. This enables us to distinguish between two main photocurrent generation mechanisms, the photovoltaic and photothermoelectric effect. We find that the dominant mechanism depends on the defined gate configuration. In the PN and NP configurations, photocurrent is mainly generated by the photovoltaic effect and the device displays a maximum responsivity of 0.70 mA/W at 532 nm illumination and rise and fall times close to 10 ms. Photocurrent generated by the photothermoelectric effect emerges in the PP configuration and is a factor of 2 larger than the current generated by the photovoltaic effect (in PN and NP configurations). This demonstrates that the photothermoelectric effect can play a significant role in devices based on WSe₂ where a region of strong optical absorption, caused by, for example, an asymmetry in flake thickness or optical absorption of the electrodes, generates a sizable thermal gradient upon illumination

Elucidating the Methylammonium (MA) Conformation in MAPbBr₃ Perovskite with Application in Solar Cells

Hybrid organic–inorganic perovskites, MAPbX₃ (X = halogen), containing methylammonium (MA: CH₃–NH₃⁺) in the large voids conformed by the PbX₆ octahedral network, are the active absorption materials in the new generation of solar cells. CH₃NH₃PbBr₃ is a promising member with a large band gap that gives rise to a high open circuit voltage. A deep knowledge of the crystal structure and, in particular, the MA conformation inside the perovskite cage across the phase transitions undergone below room temperature, seems essential to establish structure–property correlations that may drive to further improvements. The presence of protons requires the use of neutrons, combined with synchrotron XRD data that help to depict subtle symmetry changes undergone upon cooling. We present a consistent picture of the structural features of this fascinating material, in complement with photocurrent measurements from a photodetector device, demonstrating the potential of MAPbBr₃ in optoelectronics

Waveguide-Integrated MoTe₂<i>p</i>–<i>i</i>–<i>n</i> Homojunction Photodetector

Two-dimensional (2D) materials, featuring distinctive electronic and optical properties and dangling-bond-free surfaces, are promising for developing high-performance on-chip photodetectors in photonic integrated circuits. However, most of the previously reported devices operating in the photoconductive mode suffer from a high dark current or a low responsivity. Here, we demonstrate a MoTe2p–i–n homojunction fabricated directly on a silicon photonic crystal (PC) waveguide, which enables on-chip photodetection with ultralow dark current, high responsivity, and fast response speed. The adopted silicon PC waveguide is electrically split into two individual back gates to selectively dope the top regions of the MoTe2 channel in p- or n-types. High-quality reconfigurable MoTe2 (p–i–n, n–i–p, n–i–n, p–i–p) homojunctions are realized successfully, presenting rectification behaviors with ideality factors approaching 1.0 and ultralow dark currents less than 90 pA. Waveguide-assisted MoTe2 absorption promises a sensitive photodetection in the telecommunication O-band from 1260 to 1340 nm, though it is close to MoTe2’s absorption band-edge. A competitive photoresponsivity of 0.4 A/W is realized with a light on/off current ratio exceeding 104 and a record-high normalized photocurrent-to-dark-current ratio of 106 mW–1. The ultrasmall capacitance of p–i–n homojunction and high carrier mobility of MoTe2 promise a high dynamic response bandwidth close to 34.0 GHz. The proposed device geometry has the advantages of employing a silicon PC waveguide as the back gates to build a 2D material p–i–n homojunction directly and simultaneously to enhance light–2D material interaction. It provides a potential pathway to develop 2D material-based photodetectors, laser diodes, and electro-optic modulators on silicon photonic chips

Strain Control of Exciton–Phonon Coupling in Atomically Thin Semiconductors

Semiconducting transition metal dichalcogenide (TMDC) monolayers have exceptional physical properties. They show bright photoluminescence due to their unique band structure and absorb more than 10% of the light at their excitonic resonances despite their atomic thickness. At room temperature, the width of the exciton transitions is governed by the exciton–phonon interaction leading to strongly asymmetric line shapes. TMDC monolayers are also extremely flexible, sustaining mechanical strain of about 10% without breaking. The excitonic properties strongly depend on strain. For example, exciton energies of TMDC monolayers significantly redshift under uniaxial tensile strain. Here, we demonstrate that the width and the asymmetric line shape of excitonic resonances in TMDC monolayers can be controlled with applied strain. We measure photoluminescence and absorption spectra of the A exciton in monolayer MoSe₂, WSe₂, WS₂, and MoS₂ under uniaxial tensile strain. We find that the A exciton substantially narrows and becomes more symmetric for the selenium-based monolayer materials, while no change is observed for atomically thin WS₂. For MoS₂ monolayers, the line width increases. These effects are due to a modified exciton–phonon coupling at increasing strain levels because of changes in the electronic band structure of the respective monolayer materials. This interpretation based on steady-state experiments is corroborated by time-resolved photoluminescence measurements. Our results demonstrate that moderate strain values on the order of only 1% are already sufficient to globally tune the exciton–phonon interaction in TMDC monolayers and hold the promise for controlling the coupling on the nanoscale

Centimeter-Scale Synthesis of Ultrathin Layered MoO₃ by van der Waals Epitaxy

We report on the large-scale synthesis of highly oriented ultrathin MoO₃ layers using a simple and low-cost atmospheric pressure, van der Waals epitaxy growth on muscovite mica substrates. By this method, we are able to synthesize high quality centimeter-scale MoO₃ crystals with thicknesses ranging from 1.4 nm (two layers) up to a few nanometers. The crystals can be easily transferred to an arbitrary substrate (such as SiO₂) by a deterministic transfer method and be extensively characterized to demonstrate the high quality of the resulting crystal. We also study the electronic band structure of the material by density functional calculations. Interestingly, the calculations demonstrate that bulk MoO₃ has a rather weak electronic interlayer interaction, and thus, it presents a monolayer-like band structure. Finally, we demonstrate the potential of this synthesis method for optoelectronic applications by fabricating large-area field-effect devices (10 μm × 110 μm in lateral dimensions) and find responsivities of 30 mA W^–1 for a laser power density of 13 mW cm^–2 in the UV region of the spectrum and also as an electron acceptor in a MoS₂-based field-effect transistor