Long lived photogenerated charge carriers in few-layer transition metal dichalcogenides obtained from liquid phase exfoliation.

Semiconducting transition metal dichalcogenides are important optoelectronic materials thanks to their intense light-matter interaction and wide selection of fabrication techniques, with potential applications in light harvesting and sensing. Crucially, these applications depend on the lifetimes and recombination dynamics of photogenerated charge carriers, which have primarily been studied in monolayers obtained from labour-intensive mechanical exfoliation or costly chemical vapour deposition. On the other hand, liquid phase exfoliation presents a high throughput and cost-effective method to produce dispersions of mono- and few-layer nanosheets. This approach allows for easy scalability and enables the subsequent processing and formation of macroscopic films directly from the liquid phase. Here, we use transient absorption spectroscopy and spatiotemporally resolved pump-probe microscopy to study the charge carrier dynamics in tiled nanosheet films of MoS2 and WS2 deposited from the liquid phase using an adaptation of the Langmuir-Schaefer technique. We find an efficient photogeneration of charge carriers with lifetimes of several nanoseconds, which we ascribe to stabilisation at nanosheet edges. These findings provide scope for photocatalytic and photodetector applications, where long-lived charge carriers are crucial, and suggest design strategies for photovoltaic devices.

Ultrafast Umklapp-assisted electron-phonon cooling in magic-angle twisted bilayer graphene.

Understanding electron-phonon interactions is fundamentally important and has crucial implications for device applications. However, in twisted bilayer graphene near the magic angle, this understanding is currently lacking. Here, we study electron-phonon coupling using time- and frequency-resolved photovoltage measurements as direct and complementary probes of phonon-mediated hot-electron cooling. We find a remarkable speedup in cooling of twisted bilayer graphene near the magic angle: The cooling time is a few picoseconds from room temperature down to 5 kelvin, whereas in pristine bilayer graphene, cooling to phonons becomes much slower for lower temperatures. Our experimental and theoretical analysis indicates that this ultrafast cooling is a combined effect of superlattice formation with low-energy moiré phonons, spatially compressed electronic Wannier orbitals, and a reduced superlattice Brillouin zone. This enables efficient electron-phonon Umklapp scattering that overcomes electron-phonon momentum mismatch. These results establish twist angle as an effective way to control energy relaxation and electronic heat flow.

Enhanced Thermal Conductivity of Free-Standing Double-Walled Carbon Nanotube Networks.

Nanomaterials are driving advances in technology due to their oftentimes superior properties over bulk materials. In particular, their thermal properties become increasingly important as efficient heat dissipation is required to realize high-performance electronic devices, reduce energy consumption, and prevent thermal damage. One application where nanomaterials can play a crucial role is extreme ultraviolet (EUV) lithography, where pellicles that protect the photomask from particle contamination have to be transparent to EUV light, mechanically strong, and thermally conductive in order to withstand the heat associated with high-power EUV radiation. Free-standing carbon nanotube (CNT) films have emerged as candidates due to their high EUV transparency and ability to withstand heat. However, the thermal transport properties of these films are not well understood beyond bulk emissivity measurements. Here, we measure the thermal conductivity of free-standing CNT films using all-optical Raman thermometry at temperatures between 300 and 700 K. We find thermal conductivities up to 50 W m-1 K-1 for films composed of double-walled CNTs, which rises to 257 W m-1 K-1 when considering the CNT network alone. These values are remarkably high for randomly oriented CNT networks, roughly seven times that of single-walled CNT films. The enhanced thermal conduction is due to the additional wall, which likely gives rise to additional heat-carrying phonon modes and provides a certain resilience to defects. Our results demonstrate that free-standing double-walled CNT films efficiently dissipate heat, enhancing our understanding of these promising films and how they are suited to applications in EUV lithography.

Electron cooling in graphene enhanced by plasmon-hydron resonance.

Evidence is accumulating for the crucial role of a solid's free electrons in the dynamics of solid-liquid interfaces. Liquids induce electronic polarization and drive electric currents as they flow; electronic excitations, in turn, participate in hydrodynamic friction. Yet, the underlying solid-liquid interactions have been lacking a direct experimental probe. Here we study the energy transfer across liquid-graphene interfaces using ultrafast spectroscopy. The graphene electrons are heated up quasi-instantaneously by a visible excitation pulse, and the time evolution of the electronic temperature is then monitored with a terahertz pulse. We observe that water accelerates the cooling of the graphene electrons, whereas other polar liquids leave the cooling dynamics largely unaffected. A quantum theory of solid-liquid heat transfer accounts for the water-specific cooling enhancement through a resonance between the graphene surface plasmon mode and the so-called hydrons-water charge fluctuations-particularly the water libration modes, which allows for efficient energy transfer. Our results provide direct experimental evidence of a solid-liquid interaction mediated by collective modes and support the theoretically proposed mechanism for quantum friction. They further reveal a particularly large thermal boundary conductance for the water-graphene interface and suggest strategies for enhancing the thermal conductivity in graphene-based nanostructures.

Ultrafast Tunable Terahertz-to-Visible Light Conversion through Thermal Radiation from Graphene Metamaterials.

Several technologies, including photodetection, imaging, and data communication, could greatly benefit from the availability of fast and controllable conversion of terahertz (THz) light to visible light. Here, we demonstrate that the exceptional properties and dynamics of electronic heat in graphene allow for a THz-to-visible conversion, which is switchable at a sub-nanosecond time scale. We show a tunable on/off ratio of more than 30 for the emitted visible light, achieved through electrical gating using a gate voltage on the order of 1 V. We also demonstrate that a grating-graphene metamaterial leads to an increase in THz-induced emitted power in the visible range by 2 orders of magnitude. The experimental results are in agreement with a thermodynamic model that describes blackbody radiation from the electron system heated through intraband Drude absorption of THz light. These results provide a promising route toward novel functionalities of optoelectronic technologies in the THz regime.

A pre-time-zero spatiotemporal microscopy technique for the ultrasensitive determination of the thermal diffusivity of thin films.

Diffusion is one of the most ubiquitous transport phenomena in nature. Experimentally, it can be tracked by following point spreading in space and time. Here, we introduce a spatiotemporal pump-probe microscopy technique that exploits the residual spatial temperature profile obtained through the transient reflectivity when probe pulses arrive before pump pulses. This corresponds to an effective pump-probe time delay of 13 ns, determined by the repetition rate of our laser system (76 MHz). This pre-time-zero technique enables probing the diffusion of long-lived excitations created by previous pump pulses with nanometer accuracy and is particularly powerful for following in-plane heat diffusion in thin films. The particular advantage of this technique is that it enables quantifying thermal transport without requiring any material input parameters or strong heating. We demonstrate the direct determination of the thermal diffusivities of films with a thickness of around 15 nm, consisting of the layered materials MoSe2 (0.18 cm2/s), WSe2 (0.20 cm2/s), MoS2 (0.35 cm2/s), and WS2 (0.59 cm2/s). This technique paves the way for observing nanoscale thermal transport phenomena and tracking diffusion of a broad range of species.

Reversible Electrical Control of Interfacial Charge Flow across van der Waals Interfaces.

Bond-free integration of two-dimensional (2D) materials yields van der Waals (vdW) heterostructures with exotic optical and electronic properties. Manipulating the splitting and recombination of photogenerated electron-hole pairs across the vdW interface is essential for optoelectronic applications. Previous studies have unveiled the critical role of defects in trapping photogenerated charge carriers to modulate the photoconductive gain for photodetection. However, the nature and role of defects in tuning interfacial charge carrier dynamics have remained elusive. Here, we investigate the nonequilibrium charge dynamics at the graphene-WS2 vdW interface under electrochemical gating by operando optical-pump terahertz-probe spectroscopy. We report full control over charge separation states and thus photogating field direction by electrically tuning the defect occupancy. Our results show that electron occupancy of the two in-gap states, presumably originating from sulfur vacancies, can account for the observed rich interfacial charge transfer dynamics and electrically tunable photogating fields, providing microscopic insights for optimizing optoelectronic devices.

Milliwatt terahertz harmonic generation from topological insulator metamaterials.

Achieving efficient, high-power harmonic generation in the terahertz spectral domain has technological applications, for example, in sixth generation (6G) communication networks. Massless Dirac fermions possess extremely large terahertz nonlinear susceptibilities and harmonic conversion efficiencies. However, the observed maximum generated harmonic power is limited, because of saturation effects at increasing incident powers, as shown recently for graphene. Here, we demonstrate room-temperature terahertz harmonic generation in a Bi2Se3 topological insulator and topological-insulator-grating metamaterial structures with surface-selective terahertz field enhancement. We obtain a third-harmonic power approaching the milliwatt range for an incident power of 75 mW-an improvement by two orders of magnitude compared to a benchmarked graphene sample. We establish a framework in which this exceptional performance is the result of thermodynamic harmonic generation by the massless topological surface states, benefiting from ultrafast dissipation of electronic heat via surface-bulk Coulomb interactions. These results are an important step towards on-chip terahertz (opto)electronic applications.

Electrically Tunable Nonequilibrium Optical Response of Graphene.

The ability to tune the optical response of a material via electrostatic gating is crucial for optoelectronic applications, such as electro-optic modulators, saturable absorbers, optical limiters, photodetectors, and transparent electrodes. The band structure of single layer graphene (SLG), with zero-gap, linearly dispersive conduction and valence bands, enables an easy control of the Fermi energy, EF, and of the threshold for interband optical absorption. Here, we report the tunability of the SLG nonequilibrium optical response in the near-infrared (1000-1700 nm/0.729-1.240 eV), exploring a range of EF from -650 to 250 meV by ionic liquid gating. As EF increases from the Dirac point to the threshold for Pauli blocking of interband absorption, we observe a slow-down of the photobleaching relaxation dynamics, which we attribute to the quenching of optical phonon emission from photoexcited charge carriers. For EF exceeding the Pauli blocking threshold, photobleaching eventually turns into photoinduced absorption, because the hot electrons' excitation increases the SLG absorption. The ability to control both recovery time and sign of the nonequilibrium optical response by electrostatic gating makes SLG ideal for tunable saturable absorbers with controlled dynamics.

Unraveling Heat Transport and Dissipation in Suspended MoSe2 from Bulk to Monolayer.

Understanding heat flow in layered transition metal dichalcogenide (TMD) crystals is crucial for applications exploiting these materials. Despite significant efforts, several basic thermal transport properties of TMDs are currently not well understood, in particular how transport is affected by material thickness and the material's environment. This combined experimental-theoretical study establishes a unifying physical picture of the intrinsic lattice thermal conductivity of the representative TMD MoSe2 . Thermal conductivity measurements using Raman thermometry on a large set of clean, crystalline, suspended crystals with systematically varied thickness are combined with ab initio simulations with phonons at finite temperature. The results show that phonon dispersions and lifetimes change strongly with thickness, yet the thinnest TMD films exhibit an in-plane thermal conductivity that is only marginally smaller than that of bulk crystals. This is the result of compensating phonon contributions, in particular heat-carrying modes around ≈0.1 THz in (sub)nanometer thin films, with a surprisingly long mean free path of several micrometers. This behavior arises directly from the layered nature of the material. Furthermore, out-of-plane heat dissipation to air molecules is remarkably efficient, in particular for the thinnest crystals, increasing the apparent thermal conductivity of monolayer MoSe2 by an order of magnitude. These results are crucial for the design of (flexible) TMD-based (opto-)electronic applications.

Observation of giant and tunable thermal diffusivity of a Dirac fluid at room temperature.

Conducting materials typically exhibit either diffusive or ballistic charge transport. When electron-electron interactions dominate, a hydrodynamic regime with viscous charge flow emerges1-13. More stringent conditions eventually yield a quantum-critical Dirac-fluid regime, where electronic heat can flow more efficiently than charge14-22. However, observing and controlling the flow of electronic heat in the hydrodynamic regime at room temperature has so far remained elusive. Here we observe heat transport in graphene in the diffusive and hydrodynamic regimes, and report a controllable transition to the Dirac-fluid regime at room temperature, using carrier temperature and carrier density as control knobs. We introduce the technique of spatiotemporal thermoelectric microscopy with femtosecond temporal and nanometre spatial resolution, which allows for tracking electronic heat spreading. In the diffusive regime, we find a thermal diffusivity of roughly 2,000 cm2 s-1, consistent with charge transport. Moreover, within the hydrodynamic time window before momentum relaxation, we observe heat spreading corresponding to a giant diffusivity up to 70,000 cm2 s-1, indicative of a Dirac fluid. Our results offer the possibility of further exploration of these interesting physical phenomena and their potential applications in nanoscale thermal management.

Hot-Carrier Cooling in High-Quality Graphene Is Intrinsically Limited by Optical Phonons.

Many promising optoelectronic devices, such as broadband photodetectors, nonlinear frequency converters, and building blocks for data communication systems, exploit photoexcited charge carriers in graphene. For these systems, it is essential to understand the relaxation dynamics after photoexcitation. These dynamics contain a sub-100 fs thermalization phase, which occurs through carrier-carrier scattering and leads to a carrier distribution with an elevated temperature. This is followed by a picosecond cooling phase, where different phonon systems play a role: graphene acoustic and optical phonons, and substrate phonons. Here, we address the cooling pathway of two technologically relevant systems, both consisting of high-quality graphene with a mobility >10 000 cm2 V-1 s-1 and environments that do not efficiently take up electronic heat from graphene: WSe2-encapsulated graphene and suspended graphene. We study the cooling dynamics using ultrafast pump-probe spectroscopy at room temperature. Cooling via disorder-assisted acoustic phonon scattering and out-of-plane heat transfer to substrate phonons is relatively inefficient in these systems, suggesting a cooling time of tens of picoseconds. However, we observe much faster cooling, on a time scale of a few picoseconds. We attribute this to an intrinsic cooling mechanism, where carriers in the high-energy tail of the hot-carrier distribution emit optical phonons. This creates a permanent heat sink, as carriers efficiently rethermalize. We develop a macroscopic model that explains the observed dynamics, where cooling is eventually limited by optical-to-acoustic phonon coupling. These fundamental insights will guide the development of graphene-based optoelectronic devices.

Thickness-Dependent Elastic Softening of Few-Layer Free-Standing MoSe2.

Few-layer van der Waals (vdW) materials have been extensively investigated in terms of their exceptional electronic, optoelectronic, optical, and thermal properties. Simultaneously, a complete evaluation of their mechanical properties remains an undeniable challenge due to the small lateral sizes of samples and the limitations of experimental tools. In particular, there is no systematic experimental study providing unambiguous evidence on whether the reduction of vdW thickness down to few layers results in elastic softening or stiffening with respect to the bulk. In this work, micro-Brillouin light scattering is employed to investigate the anisotropic elastic properties of single-crystal free-standing 2H-MoSe2 as a function of thickness, down to three molecular layers. The so-called elastic size effect, that is, significant and systematic elastic softening of the material with decreasing numbers of layers is reported. In addition, this approach allows for a complete mechanical examination of few-layer membranes, that is, their elasticity, residual stress, and thickness, which can be easily extended to other vdW materials. The presented results shed new light on the ongoing debate on the elastic size-effect and are relevant for performance and durability of implementation of vdW materials as resonators, optoelectronic, and thermoelectric devices.

Hot carriers in graphene - fundamentals and applications.

Hot charge carriers in graphene exhibit fascinating physical phenomena, whose understanding has improved greatly over the past decade. They have distinctly different physical properties compared to, for example, hot carriers in conventional metals. This is predominantly the result of graphene's linear energy-momentum dispersion, its phonon properties, its all-interface character, and the tunability of its carrier density down to very small values, and from electron- to hole-doping. Since a few years, we have witnessed an increasing interest in technological applications enabled by hot carriers in graphene. Of particular interest are optical and optoelectronic applications, where hot carriers are used to detect (photodetection), convert (nonlinear photonics), or emit (luminescence) light. Graphene-enabled systems in these application areas could find widespread use and have a disruptive impact, for example in the field of data communication, high-frequency electronics, and industrial quality control. The aim of this review is to provide an overview of the most relevant physics and working principles that are relevant for applications exploiting hot carriers in graphene.

Electrical tunability of terahertz nonlinearity in graphene.

Graphene is conceivably the most nonlinear optoelectronic material we know. Its nonlinear optical coefficients in the terahertz frequency range surpass those of other materials by many orders of magnitude. Here, we show that the terahertz nonlinearity of graphene, both for ultrashort single-cycle and quasi-monochromatic multicycle input terahertz signals, can be efficiently controlled using electrical gating, with gating voltages as low as a few volts. For example, optimal electrical gating enhances the power conversion efficiency in terahertz third-harmonic generation in graphene by about two orders of magnitude. Our experimental results are in quantitative agreement with a physical model of the graphene nonlinearity, describing the time-dependent thermodynamic balance maintained within the electronic population of graphene during interaction with ultrafast electric fields. Our results can serve as a basis for straightforward and accurate design of devices and applications for efficient electronic signal processing in graphene at ultrahigh frequencies.

Long-lived charge separation following pump-wavelength-dependent ultrafast charge transfer in graphene/WS2 heterostructures.

Van der Waals heterostructures consisting of graphene and transition metal dichalcogenides have shown great promise for optoelectronic applications. However, an in-depth understanding of the critical processes for device operation, namely, interfacial charge transfer (CT) and recombination, has so far remained elusive. Here, we investigate these processes in graphene-WS2 heterostructures by complementarily probing the ultrafast terahertz photoconductivity in graphene and the transient absorption dynamics in WS2 following photoexcitation. We observe that separated charges in the heterostructure following CT live extremely long: beyond 1 ns, in contrast to ~1 ps charge separation reported in previous studies. This leads to efficient photogating of graphene. Furthermore, for the CT process across graphene-WS2 interfaces, we find that it occurs via photo-thermionic emission for sub-A-exciton excitations and direct hole transfer from WS2 to the valence band of graphene for above-A-exciton excitations. These findings provide insights to further optimize the performance of optoelectronic devices, in particular photodetection.

Grating-Graphene Metamaterial as a Platform for Terahertz Nonlinear Photonics.

Nonlinear optics is an increasingly important field for scientific and technological applications, owing to its relevance and potential for optical and optoelectronic technologies. Currently, there is an active search for suitable nonlinear material systems with efficient conversion and a small material footprint. Ideally, the material system should allow for chip integration and room-temperature operation. Two-dimensional materials are highly interesting in this regard. Particularly promising is graphene, which has demonstrated an exceptionally large nonlinearity in the terahertz regime. Yet, the light-matter interaction length in two-dimensional materials is inherently minimal, thus limiting the overall nonlinear optical conversion efficiency. Here, we overcome this challenge using a metamaterial platform that combines graphene with a photonic grating structure providing field enhancement. We measure terahertz third-harmonic generation in this metamaterial and obtain an effective third-order nonlinear susceptibility with a magnitude as large as 3 × 10-8 m2/V2, or 21 esu, for a fundamental frequency of 0.7 THz. This nonlinearity is 50 times larger than what we obtain for graphene without grating. Such an enhancement corresponds to a third-harmonic signal with an intensity that is 3 orders of magnitude larger due to the grating. Moreover, we demonstrate a field conversion efficiency for the third harmonic of up to ∼1% using a moderate field strength of ∼30 kV/cm. Finally, we show that harmonics beyond the third are enhanced even more strongly, allowing us to observe signatures of up to the ninth harmonic. Grating-graphene metamaterials thus constitute an outstanding platform for commercially viable, CMOS-compatible, room-temperature, chip-integrated, THz nonlinear conversion applications.

Plasmonic antenna coupling to hyperbolic phonon-polaritons for sensitive and fast mid-infrared photodetection with graphene.

Integrating and manipulating the nano-optoelectronic properties of Van der Waals heterostructures can enable unprecedented platforms for photodetection and sensing. The main challenge of infrared photodetectors is to funnel the light into a small nanoscale active area and efficiently convert it into an electrical signal. Here, we overcome all of those challenges in one device, by efficient coupling of a plasmonic antenna to hyperbolic phonon-polaritons in hexagonal-BN to highly concentrate mid-infrared light into a graphene pn-junction. We balance the interplay of the absorption, electrical and thermal conductivity of graphene via the device geometry. This approach yields remarkable device performance featuring room temperature high sensitivity (NEP of 82 pW[Formula: see text]) and fast rise time of 17 nanoseconds (setup-limited), among others, hence achieving a combination currently not present in the state-of-the-art graphene and commercial mid-infrared detectors. We also develop a multiphysics model that shows very good quantitative agreement with our experimental results and reveals the different contributions to our photoresponse, thus paving the way for further improvement of these types of photodetectors even beyond mid-infrared range.