MXenes with ordered triatomic-layer borate polyanion terminations.

Surface terminations profoundly influence the intrinsic properties of MXenes, but existing terminations are limited to monoatomic layers or simple groups, showing disordered arrangements and inferior stability. Here we present the synthesis of MXenes with triatomic-layer borate polyanion terminations (OBO terminations) through a flux-assisted eutectic molten etching approach. During the synthesis, Lewis acidic salts act as the etching agent to obtain the MXene backbone, while borax generates BO2- species, which cap the MXene surface with an O-B-O configuration. In contrast to conventional chlorine/oxygen-terminated Nb2C with localized charge transport, OBO-terminated Nb2C features band transport described by the Drude model, exhibiting a 15-fold increase in electrical conductivity and a 10-fold improvement in charge mobility at the d.c. limit. This transition is attributed to surface ordering that effectively mitigates charge carrier backscattering and trapping. Additionally, OBO terminations provide Ti3C2 MXene with substantially enriched Li+-hosting sites and thereby a large charge-storage capacity of 420 mAh g-1. Our findings illustrate the potential of intricate termination configurations in MXenes and their applications for (opto)electronics and energy storage.

Correlative Imaging of Individual CsPbBr3 Nanocrystals: Role of Isolated Grains in Photoluminescence of Perovskite Polycrystalline Thin Films.

We report on the optical properties of a CsPbBr3 polycrystalline thin film on a single grain level. A sample composed of isolated nanocrystals (NCs) mimicking the properties of the polycrystalline thin film grains that can be individually probed by photoluminescence spectroscopy was prepared. These NCs were analyzed using correlative microscopy allowing the examination of structural, chemical, and optical properties from identical sites. Our results show that the stoichiometry of the CsPbBr3 NCs is uniform and independent of the NCs' morphology. The photoluminescence (PL) peak emission wavelength is slightly dependent on the dimensions of NCs, with a blue shift up to 9 nm for the smallest analyzed NCs. The magnitude of the blueshift is smaller than the emission line width, thus detectable only by high-resolution PL mapping. By comparing the emission energies obtained from the experiment and a rigorous effective mass model, we can fully attribute the observed variations to the size-dependent quantum confinement effect.

Chiral Nanoparticle Chains on Inorganic Nanotube Templates.

Fabrication of chiral assemblies of plasmonic nanoparticles is a highly attractive and challenging task, with promising applications in light emission, detection, and sensing. So far, primarily organic chiral templates have been used for chirality inscription. Despite recent progress in using chiral ionic liquids in synthesis, the use of organic templates significantly limits the variety of nanoparticle preparation techniques. Here, we demonstrate the utilization of seemingly achiral inorganic nanotubes as templates for the chiral assembly of nanoparticles. We show that both metallic and dielectric nanoparticles can be attached to scroll-like chiral edges propagating on the surfaces of WS2 nanotubes. Such assembly can be performed at temperatures as high as 550 °C. This large temperature range significantly widens the portfolio of nanoparticle fabrication techniques, allowing us to demonstrate a variety of chiral nanoparticle assemblies, ranging from metals (Au, Ga), semiconductors (Ge), and compound semiconductors (GaAs) to oxides (WO3).

Plasmonic Properties of Individual Gallium Nanoparticles.

Gallium is a plasmonic material offering ultraviolet to near-infrared tunability, facile and scalable preparation, and good stability of nanoparticles. In this work, we experimentally demonstrate the link between the shape and size of individual gallium nanoparticles and their optical properties. To this end, we utilize scanning transmission electron microscopy combined with electron energy loss spectroscopy. Lens-shaped gallium nanoparticles with a diameter between 10 and 200 nm were grown directly on a silicon nitride membrane using an effusion cell developed in house that was operated under ultra-high-vacuum conditions. We have experimentally proven that they support localized surface plasmon resonances and their dipole mode can be tuned through their size from the ultraviolet to near-infrared spectral region. The measurements are supported by numerical simulations using realistic particle shapes and sizes. Our results pave the way for future applications of gallium nanoparticles such as hyperspectral absorption of sunlight in energy harvesting or plasmon-enhanced luminescence of ultraviolet emitters.

Structural color filters with compensated angle-dependent shifts.

Structural color filters use nano-sized elements to selectively transmit incident light, offering a scalable, economical, and environmentally friendly alternative to traditional pigment- and dye-based color filters. However, their structural nature makes their optical response prone to spectral shifts whenever the angle of incidence varies. We address this issue by introducing a conformal VO2 layer onto bare aluminum structural color filters. The insulator-metal transition of VO2 compensated the spectral shift of the filter's transmission at a 15° tilt with 80% efficiency. Unlike solutions that require adjustment of the filter's geometry, this method is versatile and suitable also for existing structural filters. Our findings also establish tunable materials in general as a possible solution for angle-dependent spectral shifts.

Real-Time Study of Surface-Guided Nanowire Growth by In Situ Scanning Electron Microscopy.

Surface-guided growth has proven to be an efficient approach for the production of nanowire arrays with controlled orientations and their large-scale integration into electronic and optoelectronic devices. Much has been learned about the different mechanisms of guided nanowire growth by epitaxy, graphoepitaxy, and artificial epitaxy. A model describing the kinetics of surface-guided nanowire growth has been recently reported. Yet, many aspects of the surface-guided growth process remain unclear due to a lack of its observation in real time. Here we observe how surface-guided nanowires grow in real time by in situ scanning electron microscopy (SEM). Movies of ZnSe surface-guided nanowires growing on periodically faceted substrates of annealed M-plane sapphire clearly show how the nanowires elongate along the substrate nanogrooves while pushing the catalytic Au nanodroplet forward at the tip of the nanowire. The movies reveal the timing between competing processes, such as planar vs nonplanar growth, catalyst-selective vapor-liquid-solid elongation vs nonselective vapor-solid thickening, and the effect of topographic discontinuities of the substrate on the growth direction, leading to the formation of kinks and loops. Contrary to some observations for nonplanar nanowire growth, planar nanowires are shown to elongate at a constant rate and not by jumps. A decrease in precursor concentration as it is consumed after long reaction time causes the nanowires to shrink back instead of growing, thus indicating that the process is reversible and takes place near equilibrium. This real-time study of surface-guided growth, enabled by in situ SEM, enables a better understanding of the formation of nanostructures on surfaces.

Low temperature 2D GaN growth on Si(111) 7 × 7 assisted by hyperthermal nitrogen ions.

As the characteristic dimensions of modern top-down devices are getting smaller, such devices reach their operational limits imposed by quantum mechanics. Thus, two-dimensional (2D) structures appear to be one of the best solutions to meet the ultimate challenges of modern optoelectronic and spintronic applications. The representative of III-V semiconductors, gallium nitride (GaN), is a great candidate for UV and high-power applications at a nanoscale level. We propose a new way of fabrication of 2D GaN on the Si(111) 7 × 7 surface using post-nitridation of Ga droplets by hyperthermal (E = 50 eV) nitrogen ions at low substrate temperatures (T < 220 °C). The deposition of Ga droplets and their post-nitridation are carried out using an effusion cell and a special atom/ion beam source developed by our group, respectively. This low-temperature droplet epitaxy (LTDE) approach provides well-defined ultra-high vacuum growth conditions during the whole fabrication process resulting in unique 2D GaN nanostructures. A sharp interface between the GaN nanostructures and the silicon substrate together with a suitable elemental composition of nanostructures was confirmed by TEM. In addition, SEM, X-ray photoelectron spectroscopy (XPS), AFM and Auger microanalysis were successful in enabling a detailed characterization of the fabricated GaN nanostructures.

Plasmonic Metasurface Resonators to Enhance Terahertz Magnetic Fields for High-Frequency Electron Paramagnetic Resonance.

Nanoscale magnetic systems play a decisive role in areas ranging from biology to spintronics. Although, in principle, THz electron paramagnetic resonance (EPR) provides high-resolution access to their properties, lack of sensitivity has precluded realizing this potential. To resolve this issue, the principle of plasmonic enhancement of electromagnetic fields that is used in electric dipole spectroscopies with great success is exploited, and a new type of resonators for the enhancement of THz magnetic fields in a microscopic volume is proposed. A resonator composed of an array of diabolo antennas with a back-reflecting mirror is designed and fabricated. Simulations and THz EPR measurements demonstrate a 30-fold signal increase for thin film samples. This enhancement factor increases to a theoretical value of 7500 for samples confined to the active region of the antennas. These findings open the door to the elucidation of fundamental processes in nanoscale samples, including junctions in spintronic devices or biological membranes.

Plasmon-induced trap filling at grain boundaries in perovskite solar cells.

The deep-level traps induced by charged defects at the grain boundaries (GBs) of polycrystalline organic-inorganic halide perovskite (OIHP) films serve as major recombination centres, which limit the device performance. Herein, we incorporate specially designed poly(3-aminothiophenol)-coated gold (Au@PAT) nanoparticles into the perovskite absorber, in order to examine the influence of plasmonic resonance on carrier dynamics in perovskite solar cells. Local changes in the photophysical properties of the OIHP films reveal that plasmon excitation could fill trap sites at the GB region through photo-brightening, whereas transient absorption spectroscopy and density functional theory calculations correlate this photo-brightening of trap states with plasmon-induced interfacial processes. As a result, the device achieved the best efficiency of 22.0% with robust operational stability. Our work provides unambiguous evidence for plasmon-induced trap occupation in OIHP and reveals that plasmonic nanostructures may be one type of efficient additives to overcome the recombination losses in perovskite solar cells and thin-film solar cells in general.

Single-Shot Three-Dimensional Orientation Imaging of Nanorods Using Spin to Orbital Angular Momentum Conversion.

The key information about any nanoscale system relates to the orientations and conformations of its parts. Unfortunately, these details are often hidden below the diffraction limit, and elaborate techniques must be used to optically probe them. Here we present imaging of the 3D rotation motion of metal nanorods, restoring the distinct nanorod orientations in the full extent of azimuthal and polar angles. The nanorods imprint their 3D orientation onto the geometric phase and space-variant polarization of the light they scatter. We manipulate the light angular momentum and generate optical vortices that create self-interference images providing the nanorods' angles via digital processing. After calibration by scanning electron microscopy, we demonstrated time-resolved 3D orientation imaging of sub-100 nm nanorods under Brownian motion (frame rate up to 500 fps). We also succeeded in imaging nanorods as nanoprobes in live-cell imaging and reconstructed their 3D rotational movement during interaction with the cell membrane (100 fps).

Kinetics of Guided Growth of Horizontal GaN Nanowires on Flat and Faceted Sapphire Surfaces.

The bottom-up assembly of nanowires facilitates the control of their dimensions, structure, orientation and physical properties. Surface-guided growth of planar nanowires has been shown to enable their assembly and alignment on substrates during growth, thus eliminating the need for additional post-growth processes. However, accurate control and understanding of the growth of the planar nanowires were achieved only recently, and only for ZnSe and ZnS nanowires. Here, we study the growth kinetics of surface-guided planar GaN nanowires on flat and faceted sapphire surfaces, based on the previous growth model. The data are fully consistent with the same model, presenting two limiting regimes-either the Gibbs-Thomson effect controlling the growth of the thinner nanowires or surface diffusion controlling the growth of thicker ones. The results are qualitatively compared with other semiconductors surface-guided planar nanowires materials, demonstrating the generality of the growth mechanism. The rational approach enabled by this general model provides better control of the nanowire (NW) dimensions and expands the range of materials systems and possible application of NW-based devices in nanotechnology.

Structural and optical properties of monocrystalline and polycrystalline gold plasmonic nanorods.

The quality of lithographically prepared structures is intimately related to the properties of the metal film from which they are fabricated. Here we compare two kinds of thin gold films on a silicon nitride membrane: a conventional polycrystalline thin film deposited by magnetron sputtering and monocrystalline gold microplates that were chemically synthesised directly on the membrane's surface for the first time. Both pristine metals were used to fabricate plasmonic nanorods using focused ion beam lithography. The structural and optical properties of the nanorods were characterized by analytical transmission electron microscopy including electron energy loss spectroscopy. The dimensions of the nanorods in both substrates reproduced well the designed size of 240×80 nm2 with the deviations up to 20 nm in both length and width. The shape reproducibility was considerably improved among monocrystalline nanorods fabricated from the same microplate. Interestingly, monocrystalline nanorods featured inclined boundaries while the boundaries of the polycrystalline nanorods were upright. Q factors and peak loss probabilities of the modes in both structures are within the experimental uncertainty identical. We demonstrate that the optical response of the plasmonic nanorods is not deteriorated when the polycrystalline metal is used instead of the monocrystalline metal.

Mechanism and Suppression of Physisorbed-Water-Caused Hysteresis in Graphene FET Sensors.

Hysteresis is a problem in field-effect transistors (FETs) often caused by defects and charge traps inside a gate isolating (e.g., SiO2) layer. This work shows that graphene-based FETs also exhibit hysteresis due to water physisorbed on top of graphene determined by the relative humidity level, which naturally happens in biosensors and ambient operating sensors. The hysteresis effect is explained by trapping of electrons by physisorbed water, and it is shown that this hysteresis can be suppressed using short pulses of alternating gate voltages.

Collector Droplet Behavior during Formation of Nanowire Junctions.

Formation of nanowire networks is an appealing strategy for demonstrating novel phenomena at the nanoscale, e.g., detection of Majorana Fermions, as well as an essential step in realizing complex nanowire-based architectures. However, a detailed description of mechanisms taking place during growth of such complex structures is lacking. Here, the experimental observations of gold-catalyzed germanium nanowire junction formation are explained utilizing phase field modeling corroborated with real-time in situ scanning electron microscopy. When the two nanowires collide head on during the growth, we observe two scenarios. (i) Two catalytic droplets merge into one, and the growth continues as a single nanowire. (ii) The droplets merge and subsequently split again, giving rise to the growth of two daughter nanowires. Both the experiments and modeling indicate the critical importance of the liquid-solid growth interface anisotropy and the growth kinetics in facilitating the structural transition during the nanowire merging process.

Influence of experimental conditions on localized surface plasmon resonances measurement by electron energy loss spectroscopy.

Scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS) has become a standard technique to map localized surface plasmon resonances with a nanometer spatial and a sufficient energy resolution over the last 15 years. However, no experimental work discussing the influence of experimental conditions during the measurement has been published up to now. We present an experimental study of the influence of the primary beam energy and the collection semi-angle on the plasmon resonances measurement by STEM-EELS. To explore the influence of these two experimental parameters we study a series of gold rods and gold bow-tie and diabolo antennas. We discuss the impact on experimental characteristics which are important for successful detection of the plasmon peak in EELS, namely: the intensity of plasmonic signal, the signal to background ratio, and the signal to zero-loss peak ratio. We found that the primary beam energy should be high enough to suppress the scattering in the sample and at the same time should be low enough to avoid the appearance of relativistic effects. Consequently, the best results are obtained using a medium primary beam energy, in our case 120 keV, and an arbitrary collection semi-angle, as it is not a critical parameter at this primary beam energy. Our instructive overview will help microscopists in the field of plasmonics to arrange their experiments.

Vacuum Rabi splitting of a dark plasmonic cavity mode revealed by fast electrons.

Recent years have seen a growing interest in strong coupling between plasmons and excitons, as a way to generate new quantum optical testbeds and influence chemical dynamics and reactivity. Strong coupling to bright plasmonic modes has been achieved even with single quantum emitters. Dark plasmonic modes fare better in some applications due to longer lifetimes, but are difficult to probe as they are subradiant. Here, we apply electron energy loss (EEL) spectroscopy to demonstrate that a dark mode of an individual plasmonic bowtie can interact with a small number of quantum emitters, as evidenced by Rabi-split spectra. Coupling strengths of up to 85 meV place the bowtie-emitter devices at the onset of the strong coupling regime. Remarkably, the coupling occurs at the periphery of the bowtie gaps, even while the electron beam probes their center. Our findings pave the way for using EEL spectroscopy to study exciton-plasmon interactions involving non-emissive photonic modes.

In Situ Variable-Temperature Scanning Tunneling Microscopy Studies of Graphene Growth Using Benzene on Pd(111).

Using a combination of in situ ultrahigh-vacuum variable-temperature scanning tunneling microscopy, ex situ Raman spectroscopy, and scanning electron microscopy, we investigated the growth of graphene using benzene on Pd(111) at temperatures up to 1100 K. Benzene adsorbs readily on Pd(111) at room temperature and forms an ordered superstructure upon annealing at 473 K. Exposure to benzene at 673 K enhances Pd step motion and yields primarily amorphous carbon upon cooling to room temperature. Monolayer graphene domains, 10-30 nm in size, appear during annealing this sample at 873 K. Dosing benzene at 1100 K results in graphene domains with varying degrees of crystallinity, while post-deposition annealing at 1100 K for 1200 s yields monolayer graphene domains larger than 150 × 150 nm2. Our results, which indicate that graphene growth on Pd(111) using benzene requires deposition/annealing temperatures higher than 673 K, are in striking contrast with the reported growth of graphene using benzene at temperatures as low as 373 K on relatively inert Cu surfaces.

High-Resolution Quantitative Phase Imaging of Plasmonic Metasurfaces with Sensitivity down to a Single Nanoantenna.

Optical metasurfaces have emerged as a new generation of building blocks for multifunctional optics. Design and realization of metasurface elements place ever-increasing demands on accurate assessment of phase alterations introduced by complex nanoantenna arrays, a process referred to as quantitative phase imaging. Despite considerable effort, the widefield (nonscanning) phase imaging that would approach resolution limits of optical microscopy and indicate the response of a single nanoantenna still remains a challenge. Here, we report on a new strategy in incoherent holographic imaging of metasurfaces, in which unprecedented spatial resolution and light sensitivity are achieved by taking full advantage of the polarization selective control of light through the geometric (Pancharatnam-Berry) phase. The measurement is carried out in an inherently stable common-path setup composed of a standard optical microscope and an add-on imaging module. Phase information is acquired from the mutual coherence function attainable in records created in broadband spatially incoherent light by the self-interference of scattered and leakage light coming from the metasurface. In calibration measurements, the phase was mapped with the precision and spatial background noise better than 0.01 and 0.05 rad, respectively. The imaging excels at the high spatial resolution that was demonstrated experimentally by the precise amplitude and phase restoration of vortex metalenses and a metasurface grating with 833 lines/mm. Thanks to superior light sensitivity of the method, we demonstrated for the first time to our knowledge the widefield measurement of the phase altered by a single nanoantenna while maintaining the precision well below 0.15 rad.

Near-field digital holography: a tool for plasmon phase imaging.

The knowledge of the phase distribution of the near electromagnetic field has become very important for many applications. However, its experimental observation is still technologically a very demanding task. In this work, we propose a novel method for the measurement of the phase distribution of the near electric field based on the principles of phase-shifting digital holography. In contrast to previous methods the holographic interference occurs already in the near field and the phase distribution can be determined purely from the scanning near-field optical microscopy measurements without the need for additional far-field interferometric methods. This opens a way towards on-chip phase imaging. We demonstrate the capabilities of the proposed method by reconstruction of the phase difference between interfering surface plasmon waves and by imaging the phase of a single surface plasmon wave. We also demonstrate a selectivity of the method towards individual components of the field.