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Charge transfer is a fundamental interface process that can be harnessed for light detection, photovoltaics, and photosynthesis. Recently, charge transfer was exploited in nanophotonics to alter plasmon polaritons by involving additional non-polaritonic materials to activate the charge transfer. Yet, direct charge transfer between polaritonic materials has not been demonstrated. We report the direct charge transfer in pure polaritonic van der Waals (vdW) heterostructures of α-MoO3/graphene. We extracted the Fermi energy of 0.6 eV for graphene by infrared nano-imaging of charge transfer hyperbolic polaritons in the vdW heterostructure. This unusually high Fermi energy is attributed to the charge transfer between graphene and α-MoO3. Moreover, we have observed charge transfer hyperbolic polaritons in multiple energy–momentum dispersion branches with a wavelength elongation of up to 150%. With the support from the density functional theory calculation, we find that the charge transfer between graphene and α-MoO3, absent in mechanically assembled vdW heterostructures, is attributed to the relatively pristine heterointerface preserved in the epitaxially grown vdW heterostructure. The direct charge transfer and charge transfer hyperbolic polaritons demonstrated in our work hold great promise for developing nano-optical circuits, computational devices, communication systems, and light and energy manipulation devices. [ABSTRACT FROM AUTHOR]

Plasmonic nanoantennas show significant potential in photodetection applications, but the extent to which their full potential can be realized is dictated by the volume and location of the active materials within the plasmonic structure. Carbon nanotubes (CNTs) have been used as a novel material in photodetection application due to their excellent electronic and optoelectronic properties. However, difficulties in the integration of CNTs in the gaps of nanoantennas have limited the investigation of antenna-coupled CNT detectors. Here, we demonstrate a unique plasmonic approach for selectively growing CNTs in the gap of nanoantenna arrays for fabrication of plasmonic infrared bolometers operating at room temperature. Strong concentration of light at the tips of nanoantennas was utilized for localized heating and growth of CNTs. Moreover, interaction of this strong optical field with the small volume of CNTs enhanced the photoresponse of the bolometers. Consequently, a high responsivity of about 800 V W-1 was achieved at room temperature. [ABSTRACT FROM AUTHOR]

Polar van der Waals (vdW) crystals, composed of atomic layers held together by vdW forces, can host phonon polaritons-quasiparticles arising from the interaction between photons in free-space light and lattice vibrations in polar materials. These crystals offer advantages such as easy fabrication, low Ohmic loss, and optical confinement. Recently, hexagonal boron nitride (hBN), known for having hyperbolicity in the mid-infrared range, has been used to explore multiple modes with high optical confinement. This opens possibilities for practical polaritonic nanodevices with subdiffractional resolution. However, polariton waves still face exposure to the surrounding environment, leading to significant energy losses. In this work, we propose a simple approach to inducing a hyperbolic phonon polariton (HPhP) waveguide in hBN by incorporating a low dielectric medium, ZrS 2 . The low dielectric medium serves a dual purpose-it acts as a pathway for polariton propagation, while inducing high optical confinement. We establish the criteria for the HPhP waveguide in vdW heterostructures with various thicknesses of ZrS 2 through scattering-type scanning near-field optical microscopy (s-SNOM) and by conducting numerical electromagnetic simulations. Our work presents a feasible and straightforward method for developing practical nanophotonic devices with low optical loss and high confinement, with potential applications such as energy transfer, nano-optical integrated circuits, light trapping, etc.

The interest in the wafer-scale growth of two-dimensional (2D) materials, including transition metal dichalcogenides (TMDCs), has been rising for transitioning from lab-scale devices to commercial-scale systems. Among various synthesis techniques, physical vapor deposition, such as pulsed laser deposition (PLD), has shown promise for the wafer-scale growth of 2D materials. However, due to the high volatility of chalcogen atoms (e.g., S and Se), films deposited by PLD usually suffer from a lack of stoichiometry and chalcogen deficiency. To mitigate this issue, excess chalcogen is necessary during the deposition, which results in problems like uniformity or not being repeatable. This study demonstrates a condensed-phase or amorphous phase-mediated crystallization (APMC) approach for the wafer-scale synthesis of 2D materials. This method uses a room-temperature PLD process for the deposition and formation of amorphous precursors with controlled thicknesses, followed by a post-deposition crystallization process to convert the amorphous materials to crystalline structures. This approach maintains the stoichiometry of the deposited materials throughout the deposition and crystallization process and enables the large-scale synthesis of crystalline 2D materials (e.g., MoS 2 and WSe 2 ) on Si/SiO 2 substrates, which is critical for future wafer-scale electronics. We show that the thickness of the layers can be digitally controlled by the number of laser pulses during the PLD phase. Optical spectroscopy is used to monitor the crystallization dynamics of amorphous layers as a function of annealing temperature. The crystalline quality, domain sizes, and the number of layers were explored using nanoscale and atomistic characterization (e.g., AFM, STEM, and EDS) along with electrical characterization to explore process-structure-performance relationships. This growth technique is a promising method that could potentially be adopted in conventional semiconductor industries for wafer-scale manufacturing of next-generation electronic and optoelectronic devices.

Understanding and controlling the growth evolution of atomically thin monolayer two-dimensional (2D) materials such as transition metal dichalcogenides (TMDCs) are vital for next-generation 2D electronics and optoelectronic devices. However, their growth kinetics are not fully observed or well understood due to the bottlenecks associated with the existing synthesis methods. This study demonstrates the time-resolved and ultrafast growth of 2D materials by a laser-based synthesis approach that enables the rapid initiation and termination of the vaporization process during crystal growth. The use of stoichiometric powder (e.g., WSe 2 ) minimizes the complex chemistry during the vaporization and growth process, allowing rapid initiation/termination control over the generated flux. An extensive set of experiments is performed to understand the growth evolution, achieving subsecond growth as low as 10 ms along with a 100 μm/s growth rate on a noncatalytic substrate such as Si/SiO 2 . Overall, this study allows us to observe and understand the 2D crystal evolution and growth kinetics with time-resolved and subsecond time scales.

Titanium is widely used in medical devices, such as dental and orthopedic implants, due to its excellent mechanical properties, low toxicity, and biocompatibility. However, the titanium surface has the risk of microbial biofilm formation, which results in infections from species such as Candida albicans ( C. albicans ). This kind of biofilm prevents antifungal therapy and complicates the treatment of infectious diseases associated with implanted devices. It is critical to developing a feasible surface to decrease microbial growth while not interfering with the growth of the host cells. This study reports the influence of titanium surface modification to titanium disulfide (TiS 2 ) on inhibiting C. albicans biofilm formation while allowing the attachment of human gingival fibroblasts (HGFs) on their surface. The surface of titanium parts is directly converted to structured titanium and TiS 2 using direct laser processing and crystal growth methods. C. albicans adhesion and colonization are then investigated on these surfaces by the colony counting assay and reactive oxygen species (ROS) assay, using 2',7'-dichlorofluorescin diacetate (DCFH-DA) and microscopy images. Also, the viability and adhesion of HGFs on these surfaces are investigated to show their adhesion and biocompatibility. Titanium samples with the TiS 2 surface show both C. albicans biofilm inhibition and HGF attachment. This study provides insight into designing and manufacturing titanium biomedical implants.

This work presents a novel, to the best of our knowledge, cross correlation technique for determining the laser heating-induced Raman shift laser power coefficient ψ required for energy transport state-resolved Raman (ET-Raman) methods. The cross correlation method determines the measure of similarity between the experimental intensity data and a varying test Gaussian signal. By circumventing the errors inherent in any curve fittings, the cross correlation method quickly and accurately determines the location where the test Gaussian signal peak is most like the Raman peak, thereby revealing the peak location and ultimately the value of ψ. This method improves the reliability of optothermal Raman-based methods for micro/nanoscale thermal measurements and offers a robust approach to data processing through a global treatment of Raman spectra.

Strain-engineering in 2D transition metal dichalcogenide (TMD) semiconductors has garnered intense research interest in tailoring the optical properties via strain-induced modifications of the electronic bands in TMDs, while its impact on the exciton dynamics remains less understood. To address this, an extensive study of transient optical absorption (TA) of both W- and Mo-based single-crystalline monolayer TMDs grown by a recently developed laser-assisted evaporation method is performed. All spectral features of the monolayers as grown on fused silica substrates exhibit appreciable redshifts relating to the existence of strain due to growth conditions. Moreover, these systems exhibit a dramatic slowing down of exciton dynamics (100s of picoseconds to few nanoseconds) with an increase in carrier densities, which strongly contrasts with the monolayers in their freestanding form as well as in comparison with more traditionally grown TMDs. The observations are related to the modifications of the electronic bands as expected from the strain and associated population of the intervalley dark excitons that can now interplay with intravalley excitations. These findings are consistent across both the Mo- and W-based TMD families, providing key information about the influence of the growth conditions on the nature of optical excitations and fostering emerging optoelectronic applications of monolayer TMDs., (© 2022 Wiley-VCH GmbH.)

The emergence of rapidly expanding infectious diseases such as coronavirus (COVID-19) demands effective biosensors that can promptly detect and recognize the pathogens. Field-effect transistors based on semiconducting two-dimensional (2D) materials (2D-FETs) have been identified as potential candidates for rapid and label-free sensing applications. This is because any perturbation of such atomically thin 2D channels can significantly impact their electronic transport properties. Here, we report the use of FET based on semiconducting transition metal dichalcogenide (TMDC) WSe 2 as a promising biosensor for the rapid and sensitive detection of SARS-CoV-2 in vitro . The sensor is created by functionalizing the WSe 2 monolayers with a monoclonal antibody against the SARS-CoV-2 spike protein and exhibits a detection limit of down to 25 fg/μL in 0.01X phosphate-buffered saline (PBS). Comprehensive theoretical and experimental studies, including density functional theory, atomic force microscopy, Raman and photoluminescence spectroscopies, and electronic transport properties, were performed to characterize and explain the device performance. The results demonstrate that TMDC-based 2D-FETs can potentially serve as sensitive and selective biosensors for the rapid detection of infectious diseases.

Two-dimensional transition metal dichalcogenides (2D-TMDs) hold a great potential to platform future flexible optoelectronics. The beating hearts of these materials are their excitons known as X A and X B , which arise from transitions between spin-orbit split (SOS) levels in the conduction and valence bands at the K-point. The functionality of 2D-TMD-based devices is determined by the dynamics of these excitons. One of the most consequential channels of exciton decay on the device functionality is the defect-assisted recombination (DAR). Here, we employ steady-state absorption and emission spectroscopies, and pump density-dependent femtosecond transient absorption spectroscopy to report on the effect of DAR on the lifetime of excitons in monolayers of tungsten disulfide (2D-WS 2 ) and diselenide (2D-WSe 2 ). These pump-probe measurements suggested that while exciton decay dynamics in both monolayers are driven by DAR, in 2D-WS 2 , defect states near the X B exciton fill up before those near the X A exciton. However, in the 2D-WSe 2 monolayer, the defect states fill up similarly. Understanding the contribution of DAR on the lifetime of excitons and the partition of this decay channel between X A and X B excitons may open new horizons for the incorporation of 2D-TMD materials in future optoelectronics.

Direct synthesis, large-scale integration, and patterning of two-dimensional (2D) quantum materials (e.g. MoS 2 , WSe 2 ) on flexible and transparent substrates are of high interest for flexible and conformal device applications. However, the growth temperatures (e.g. 850 °C) of the emerging 2D materials in the common gas-phase synthesis methods are well beyond the tolerances limit of flexible substrates, such as polydimethylsiloxane (PDMS). In addition, random nucleation and growth process in most growth systems limits the predicted integration and patterning freedoms. Here, we report a rapid direct laser crystallization and mask-free large-scale patterning of MoS 2 and WSe 2 crystals on PDMS substrates. A thin layer of stoichiometric amorphous 2D film is first laser-deposited via pulsed laser deposition (PLD) system onto the flexible substrates followed by a controlled crystallization and direct writing process using a tunable nanosecond laser (1064 nm). The influences of pulse duration, number of pulses, and the thickness of the deposited amorphous 2D layer on the crystallization of 2D materials are discussed. Optical spectroscopy and electrical characterizations are performed to confirm the quality of crystallized 2D materials on flexible substrates. This novel method opens up a new opportunity for the crystallization of complex patterns directly from computer-aided design models for the future 2D materials-based wearable, transparent, and flexible devices.

This work reports the interfacial thermal conductance ( G ) and radiative recombination efficiency (β), also known as photoluminescence quantum yield (PL QY), of monolayer WSe 2 flakes supported by fused silica substrates via energy-transport state-resolved Raman (ET-Raman). This is the first known work to consider the effect of radiative electron-hole recombination on the thermal transport characteristics of single-layer transition-metal dichalcogenides (TMDs). ET-Raman uses a continuous-wave laser for steady-state heating as well as nanosecond and picosecond lasers for transient energy transport to simultaneously heat the monolayer flakes and extract the Raman signal. The three lasers induce distinct heating phenomena that distinguish the interfacial thermal conductance and radiative recombination efficiency, which can then be determined in tandem with three-dimensional (3D) numerical modeling of the temperature rise from respective laser irradiation. For the five samples measured, G is found to range from 2.10 ± 0.14 to 15.9 ± 5.0 MW m -2 K -1 and β ranges from 36 ± 6 to 65 ± 7%. These values support the claim that interfacial phenomena such as surface roughness and two-dimensional (2D) material-substrate bonding strength play critical roles in interfacial thermal transport and electron-hole recombination mechanisms in TMD monolayers. It is also determined that low-level defect density enhances the radiative recombination efficiency of single-layer WSe 2 .

Excitons in two-dimensional transition metal dichalcogenide monolayers (2D-TMDs) are of essential importance due to their key involvement in 2D-TMD-based applications. For instance, exciton dissociation and exciton radiative recombination are indispensible processes in photovoltaic and light-emitting devices, respectively. These two processes depend drastically on the photogeneration efficiency and lifetime of excitons. Here, we incorporate femtosecond pump-probe spectroscopy to investigate the ultrafast dynamics of exciton formation and decay in a single crystal of monolayer 2D tungsten disulfide (WS2). Investigation of the formation dynamics of the lowest exciton (XA) indicated that the formation time linearly increases from ∼150 fs upon resonant excitation, to ∼500 fs following excitation that is ∼1.1 eV above the band-gap. This dependence is attributed to the time it takes highly excited electrons in the conduction band (CB) to relax to the CB minimum (CBM) and contribute to the formation of XA. This is confirmed by infrared measurements of electron intraband relaxation dynamics. Furthermore, pump-probe experiments suggested that the XA ground state depletion recovery dynamics depend on the excitation energy as well. The average recovery time increased from ∼10 ps in the case of resonant excitation to ∼50 ps following excitation well above the band-gap. Having the ability to control whether generating short-lived or long-lived electron-hole pairs in 2D-TMD monolayers opens a new horizon for the application of these materials. For instance, long-lived electron-hole pairs are appropriate for photovoltaic devices, but short-lived excitons are more beneficial for lasers with ultrashort pulses.

Titanium has been the material of interest in biological implant applications due to its unique mechanical properties and biocompatibility. Their design is now growing rapidly due to the advent of additive manufacturing technology that enables the fabrication of complex and patient-customized parts. Titanium dioxides (TiO 2 ) coatings with different phases (e.g., anatase, rutile) and morphologies have shown to be effective in enhancing osteointegration and antibacterial behavior. This enhanced antibacterial behavior stems from the photocatalytic activity generated from crystalline TiO 2 coatings. Anatase has commonly been shown to be a more photocatalytic oxide phase compared to rutile despite its larger band gap. However, more recent studies have suggested that a synergistic effect leading to increased photocatalytic activity may be produced with a combination of oxides containing both anatase and rutile phases. Here, we demonstrate the selective and localized formation of TiO 2 nanostructures on additive and wrought titanium parts with anatase, rutile, and mixed phases by a laser-induced transformation approach. Compared to conventional coating processes, this technique produces desired TiO 2 phases simply by controlled laser irradiation of titanium parts in an oxygen environment, where needed. The effects of processing conditions such as laser power, scanning speed, laser pulse duration, frequency, and gas flow on the selective transformation were studied. The morphological and structural evolutions were investigated using various characterization techniques. This method is specifically of significant interest in creating phase-selective TiO 2 surfaces on titanium-based bioimplants, including those fabricated by additive manufacturing technologies., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Interest in layered two-dimensional (2D) materials has been escalating rapidly over the past few decades due to their promising optoelectronic and photonic properties emerging from their atomically thin 2D structural confinements. When these 2D materials are further confined in lateral dimensions toward zero-dimensional (0D) structures, 2D nanoparticles and quantum dots with new properties can be formed. Here, we report a nonequilibrium gas-phase synthesis method for the stoichiometric formation of gallium selenide (GaSe) nanoparticles ensembles that can potentially serve as quantum dots. We show that the laser ablation of a target in an argon background gas condenses the laser-generated plume, resulting in the formation of metastable nanoparticles in the gas phase. The deposition of these nanoparticles onto the substrate results in the formation of nanoparticle ensembles, which are then post-processed to crystallize or sinter the nanoparticles. The effects of background gas pressures, in addition to crystallization/sintering temperatures, are systematically studied. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, and time-correlated single-photon counting (TCSPC) measurements are used to study the correlations between growth parameters, morphology, and optical properties of the fabricated 2D nanoparticle ensembles.

Two-dimensional (2D) crystal growth over substrate features is fundamentally guided by the Gauss-Bonnet theorem, which mandates that rigid, planar crystals cannot conform to surfaces with nonzero Gaussian curvature. Here, we reveal how topographic curvature of lithographically designed substrate features govern the strain and growth dynamics of triangular WS 2 monolayer single crystals. Single crystals grow conformally without strain over deep trenches and other features with zero Gaussian curvature; however, features with nonzero Gaussian curvature can easily impart sufficient strain to initiate grain boundaries and fractured growth in different directions. Within a strain-tolerant regime, however, triangular single crystals can accommodate considerable (<1.1%) localized strain exerted by surface features that shift the bandgap up to 150 meV. Within this regime, the crystal growth accelerates in specific directions, which we describe using a growth model. These results present a previously unexplored strategy to strain-engineer the growth directions and optoelectronic properties of 2D crystals.