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Defects can locally tailor the electronic properties of 2D materials, including the band gap and electron density, and possess the merit for optical and electronic applications. However, it is still a great challenge to realize rational defect engineering, which requires quantitative study of the effect of defects on electronic properties under ambient conditions. In this work, we employed tip-enhanced photoluminescence (TEPL) spectroscopy to obtain the PL spectra of different defects (wrinkle and edge) in mechanically exfoliated thin-layer transition metal dichalcogenides (TMDCs) with nanometer spatial resolution. We quantitatively obtained the band gap and electron density at defects by analyzing the wavelength and intensity ratio of excitons and trions. We further visualized the strain distribution across a wrinkle and the edge-induced reconstructive regions of the band gap and electron density by TEPL line scans. The doping effect on the Fermi level and optical performance was unveiled through comparative studies of edges on TMDC monolayers of different doping types. These quantitative results are vital to guide defect engineering and design and fabrication of TMDC-based optoelectronics devices.

Monolayer transition-metal dichalcogenides (TMDCs) show a wealth of exciton physics. Here, we report the existence of a new excitonic species, the high-lying exciton (HX), in single-layer WSe2 with an energy of ~3.4 eV, almost twice the band-edge A-exciton energy, with a linewidth as narrow as 5.8 meV. The HX is populated through momentum-selective optical excitation in the K-valleys and is identified in upconverted photoluminescence (UPL) in the UV spectral region. Strong electron-phonon coupling results in a cascaded phonon progression with equidistant peaks in the luminescence spectrum, resolvable to ninth order. Ab initio GW-BSE calculations with full electron-hole correlations explain HX formation and unmask the admixture of upper conduction-band states to this complex many-body excitation. These calculations suggest that the HX is comprised of electrons of negative mass. The coincidence of such high-lying excitonic species at around twice the energy of band-edge excitons rationalizes the excitonic quantum-interference phenomenon recently discovered in optical second-harmonic generation (SHG) and explains the efficient Auger-like annihilation of band-edge excitons.

Monolayer semiconductors are emerging platforms for strong nonlinear light-matter interaction, which is enhanced by the giant oscillator strength of tightly bound excitons. Little attention has been paid to the impact of excitonic resonances on the temporal dynamics of nonlinear light-matter interaction, since harmonic generation and optical-wave mixing are generally considered instantaneous processes. We find that a significant time difference, ranging from -40 fs to +120 fs, is necessary between two light pulses for optimal sum-frequency generation (SFG) and four-wave mixing (FWM) to occur from monolayer WSe2 when one of the pulses is in resonance with an excitonic transition. These resonances involve both band-edge A-excitons (AX) as well as high-lying excitons (HX) comprising electrons from conduction bands far above the gap. Numerical simulations of the density-matrix evolution reproduce and explain the distinct dynamics of SFG and FWM. The interpulse delays for maximal SFG and FWM are governed primarily by the lifetime of the one-photon and two-photon resonant states, respectively. The method therefore offers an unconventional probe of excitonic dynamics that are either one-photon or two-photon allowed. Remarkably, the longest delay times occur at the lowest excitation powers, indicating a strong nonlinearity that offers exploration potential for excitonic quantum nonlinear optics.

In surface-enhanced Raman spectra, vibrational peaks are superimposed on a background continuum, which is known as one major experimental anomaly. This is problematic in assessing vibrational information especially in the low Raman-shift region below 200 cm−1, where the background signals dominate. Herein, we present a rigorous comparison of normal Raman and surface-enhanced Raman spectra for atomically defined surfaces of Au(111) or Au(100) with and without molecular adsorbates. It is clearly shown that the origin of the background continuum is well explained by a local field enhancement of electronic Raman scattering in the conduction band of Au. In the low Raman-shift region, electronic Raman scattering gains additional intensity, probably due to a relaxation in the conservation of momentum rule through momentum transfer from surface roughness. Based on the mechanism for generation of the spectral background, we also present a practical method to extract electronic and vibrational information at the metal/dielectric interface from the measured raw spectra by reducing the thermal factor, the scattering efficiency factor and the Purcell factor over wide ranges in both the Stokes and the anti-Stokes branches. This method enables us not only to analyse concealed vibrational features in the low Raman-shift region but also to estimate more reliable local temperatures from surface-enhanced Raman spectra., Both electronic and vibrational information at the metal/dielectric interface were explicitly extracted from surface-enhanced Raman spectra.

Defects can induce drastic changes of the electronic properties of two-dimensional transition metal dichalcogenides and influence their applications. It is still a great challenge to characterize small defects and correlate their structures with properties. Here, we show that tip-enhanced Raman spectroscopy (TERS) can obtain distinctly different Raman features of edge defects in atomically thin MoS2, which allows us to probe their unique electronic properties and identify defect types (e.g., armchair and zigzag edges) in ambient. We observed an edge-induced Raman peak (396 cm−1) activated by the double resonance Raman scattering (DRRS) process and revealed electron–phonon interaction in edges. We further visualize the edge-induced band bending region by using this DRRS peak and electronic transition region using the electron density-sensitive Raman peak at 406 cm−1. The power of TERS demonstrated in MoS2 can also be extended to other 2D materials, which may guide the defect engineering for desired properties. Probing inevitable defects in two- dimensional materials is challenging. Here, the authors tackle this issue by using tip-enhanced Raman spectroscopy (TERS) to obtain distinctly different Raman features of edge defects in atomically thin MoS2, and further probe their unique electronic properties as well as identify the armchair and zigzag edges.

We report about the investigation of twisted MoSe2 homo- and MoSe2–WSe2 heterobilayers by means of low-frequency Raman spectroscopy (LFRS) and low-temperature micro photoluminescence (µPL). In room-temperature LFRS experiments on both, twisted MoSe2 homobilayers and twisted MoSe2–WSe2 heterobilayers, we observe moiré phonons, i.e. folded acoustic phonon modes due to the moiré superlattice. In the heterobilayers, we can identify moiré phonons of both materials, MoSe2 and WSe2. While the twist angles for the homobilayers are relatively precisely known from the applied tear-and-stack preparation method, the twist angles of the heterobilayers have to be determined via second-harmonic-generation microscopy on monolayer regions of the samples, which has significant uncertainties. We show that by the moiré phonons of the heterobilayers, the relative twist angles can be determined on a local scale with much higher precision. We apply our technique for the investigation of a large area H-type (twist angle θ = 60∘ + δ) MoSe2–WSe2 heterobilayer. These investigations show that spatial regions, which can be identified to be atomically reconstructed (i.e. δ = 0∘) by the observation of an interlayer shear mode in LFRS experiments, exhibit a strong, momentum-allowed interlayer-exciton signal in low-temperature µPL. On the contrary, regions, where moiré phonons are observed, i.e. which can be identified to be rigidly twisted by a misalignment angle in the range of 5 ° ≲ | δ | ≲ 6 ° , exhibit no significant interlayer-exciton signals.

The dynamics of momentum-dark exciton formation in transition metal dichalcogenides is difficult to measure experimentally, as many momentum-indirect exciton states are not accessible to optical interband spectroscopy. Here, we combine a tunable pump, high-harmonic probe laser source with a 3D momentum imaging technique to map photoemitted electrons from monolayer WS

The dynamics of exciton formation in transition metal dichalcogenides is difficult to measure experimentally, since many momentum-indirect exciton states are not accessible to optical interband spectroscopy. Here, we combine a tuneable pump, high-harmonic probe laser source with a 3D momentum imaging technique to map photoemitted electrons from monolayer WS$_2$. This provides momentum-, energy- and time-resolved access to excited states on an ultrafast timescale. The high temporal resolution of the setup allows us to trace the early-stage exciton dynamics on its intrinsic timescale and observe the formation of a momentum-forbidden dark K$\Sigma$ exciton a few tens of femtoseconds after optical excitation. By tuning the excitation energy we manipulate the temporal evolution of the coherent excitonic polarization and observe its influence on the dark exciton formation. The experimental results are in excellent agreement with a fully microscopic theory, resolving the temporal and spectral dynamics of bright and dark excitons in WS$_2$., Comment: 18 pages, 5 figures

In homobilayer systems, the twist angle θ has emerged as a powerful tuning knob for tailoring novel phase transitions in atomically thin layers stacked at magic twist angles [1] – a paradigm shift for condensed-matter physics. For twisted bilayers of transition metal dichalcogenides, topological phases [2] and even potential signatures of a superconducting state [3] have been discussed. Yet, a precise understanding of the underlying Coulomb correlations has remained challenging.

Precise measurement of the temperature right at the surface of thermoplasmonic nanostructures is a grand challenge but extremely important for the photochemical reaction and photothermal therapy. We present here a method capable of measuring the surface temperature of plasmonic nanostructures with surface-enhanced Raman spectroscopy, which is not achievable by existing methods. We observe a sensitive shift of stretching vibration of a phenyl isocyanide molecule with temperature (0.232 cm–1/°C) as a result of the temperature-dependent molecular orientation change. We develop this phenomenon into a method capable of measuring the surface temperature of Au nanoparticles (NPs) during plasmonic excitation, which is validated by monitoring the laser-induced desorption process of the adsorbed CO on Au NP surface. We further extend the method into a more demanding single living cell thermometry that requires a high spatial resolution, which allows us to successfully monitor the extracellular temperature distribut...

Twist-engineering of the electronic structure in van-der-Waals layered materials relies predominantly on band hybridization between layers. Band-edge states in transition-metal-dichalcogenide semiconductors are localized around the metal atoms at the center of the three-atom layer and are therefore not particularly susceptible to twisting. Here, we report that high-lying excitons in bilayer WSe2 can be tuned over 235 meV by twisting, with a twist-angle susceptibility of 8.1 meV/°, an order of magnitude larger than that of the band-edge A-exciton. This tunability arises because the electronic states associated with upper conduction bands delocalize into the chalcogenide atoms. The effect gives control over excitonic quantum interference, revealed in selective activation and deactivation of electromagnetically induced transparency (EIT) in second-harmonic generation. Such a degree of freedom does not exist in conventional dilute atomic-gas systems, where EIT was originally established, and allows us to shape the frequency dependence, i.e., the dispersion, of the optical nonlinearity., Here, the authors report on the large twist-angle susceptibility of excitons involving upper conduction bands in transition metal dichalcogenide bilayers. These high-lying excitons couple with band-edge excitons, and give rise to nonlinear quantum-optical processes that become tuneable by twisting.

Phase-locked few-cycle mid-infrared pulses trace how the twist angle alone renormalizes the binding energy of excitons in twisted WSe2 homobilayers by a factor of two and tunes their lifetime by a factor of twenty.

By probing internal 1s-2p transitions with phase-locked mid-infrared pulses, we reveal the internal structure and binding energy of photo-generated excitons in transition metal dichalcogenide bilayers. Furthermore, we trace how the twist angle precisely controls the ultrafast formation of interlayer excitons and tunes excitonic hybridization in hetero- and homobilayers, respectively.

Underpotential deposition offers a predominant way to tailor the electronic structure of the catalytic surface at the atomic level, which is key to engineering materials with a high activity for (electro)catalysis. However, it remains challenging to precisely control and directly probe the underpotential deposition of a (sub)monolayer of atoms on nanoparticle surfaces. In this work, we in situ observe silver electrodeposited on gold nanocrystals surface from sub-monolayer to one monolayer by designing a highly sensitive electrochemical dark field scattering setup. The spectral variation is used to reconstruct the optical “cyclic voltammogram” of every single nanocrystal for understanding the underpotential deposition process on nanocrystals, which cannot be achieved by any other methods but are essential for creating novel nanomaterials., Underpotential deposition (UPD) is important to modify the surface properties of nanocrystals. Here, the authors show the application of in situ electrochemical dark field spectroscopy in identifying the UPD processes of silver on different facets of gold nanocrystals at the single nanoparticle level.

The large surface-to-volume ratio in atomically thin 2D materials allows to efficiently tune their properties through modifications of their environment. Artificial stacking of two monolayers into a bilayer leads to an overlap of layer-localized wave functions giving rise to a twist angle-dependent hybridization of excitonic states. In this joint theory-experiment study, we demonstrate the impact of interlayer hybridization on bright and momentum-dark excitons in twisted WSe2 bilayers. In particular, we show that the strong hybridization of electrons at the Λ point leads to a drastic redshift of the momentum-dark K-Λ exciton, accompanied by the emergence of flat moiré exciton bands at small twist angles. We directly compare theoretically predicted and experimentally measured optical spectra allowing us to identify photoluminescence signals stemming from phonon-assisted recombination of layer-hybridized dark excitons. Moreover, we predict the emergence of additional spectral features resulting from the moiré potential of the twisted bilayer lattice.

The large surface-to-volume ratio in atomically thin 2D materials allows to efficiently tune their properties through modifications of their environment. Artificial stacking of two monolayers into a bilayer leads to an overlap of layer-localized wave functions giving rise to a twist angle-dependent hybridization of excitonic states. In this joint theory-experiment study, we demonstrate the impact of interlayer hybridization on bright and momentum-dark excitons in twisted WSe$_2$ bilayers. In particular, we show that the strong hybridization of electrons at the $\Lambda$ point leads to a drastic redshift of the momentum-dark K-$\Lambda$ exciton, accompanied by the emergence of flat moir\'e exciton bands at small twist angles. We directly compare theoretically predicted and experimentally measured optical spectra allowing us to identify photoluminescence signals stemming from phonon-assisted recombination of layer-hybridized dark excitons. Moreover, we predict the emergence of additional spectral features resulting from the moir\'e potential of the twisted bilayer lattice.

The recent discovery of artificial phase transitions induced by stacking monolayer materials at magic twist angles represents a paradigm shift for solid state physics. Twist-induced changes of the single-particle band structure have been studied extensively, yet a precise understanding of the underlying Coulomb correlations has remained challenging. Here we reveal in experiment and theory, how the twist angle alone affects the Coulomb-induced internal structure and mutual interactions of excitons. In homobilayers of WSe2, we trace the internal 1s–2p resonance of excitons with phase-locked mid-infrared pulses as a function of the twist angle. Remarkably, the exciton binding energy is renormalized by up to a factor of two, their lifetime exhibits an enhancement by more than an order of magnitude, and the exciton-exciton interaction is widely tunable. Our work opens the possibility of tailoring quasiparticles in search of unexplored phases of matter in a broad range of van der Waals heterostructures., The crystallographic orientation of monolayers in van der Waals multi-layers controls their electronic and optical properties. Here the authors show how the twist angle affects Coulomb correlations governing the internal structure and the mutual interaction of excitons in homobilayers of WSe2.

Electromagnetically induced transparency (EIT) arises because of quantum interference between electronic transitions. While the phenomenon is a “gold standard” in atomic quantum optics, it is hard to probe in bulk condensed matter and difficult to control in quantum-confined systems—prerequisites for exploitation in devices. EIT arises in excitonic transitions of single-layer transition-metal dichalcogenide crystals, which, in effect, constitute giant two-dimensional exfoliated molecules. We exploit the characteristic sensitivity of molecules to their immediate dielectric environment to demonstrate how chemical tuning of the exciton resonance over 5% of the exciton energy allows unprecedented control over quantum interference. EIT is probed in second-harmonic generation (SHG) of monolayer WSe2, where it gives rise to resonant suppression of SHG in response to the immediate surrounding. This solid-state solvatochromic effect arises primarily from changes in electronic band gap and exciton binding energy of monolayer WSe2. Surprisingly, the EIT resonance shifts linearly with exciton energy in response to the dielectric nonlocal manipulation. The approach demonstrates that concepts from atomic quantum optics can be ported directly to condensed-phase materials, stimulating synthetic challenges to develop materials to tune quantum-coherent phenomena.

Tip-enhanced Raman spectroscopy (TERS), known as nanospectroscopy, has received increasing interest as it can provide nanometer spatial resolution and chemical fingerprint information of samples simultaneously. Since Ag tips are well accepted to show a higher TERS enhancement than that of gold tips, there is an urgent quest for Ag TERS tips with a high enhancement, long lifetime, and high reproducibility, especially for atomic force microscopy (AFM)-based TERS. Herein, we developed an electrodeposition method to fabricate Ag-coated AFM TERS tips in a highly controllable and reproducible way. We investigated the influence of the electrodeposition potential and time on the morphology and radius of the tip. The radii of Ag-coated AFM tips can be rationally controlled at a few to hundreds nanometers, which allows us to systematically study the dependence of the TERS enhancement on the tip radius. The Ag-coated AFM tips show the highest TERS enhancement under 632.8 nm laser excitation and a broad localized surface plasmon resonance (LSPR) response when coupled to a Au substrate. The tips exhibit a lifetime of 13 days, which is particularly important for applications that need a long measuring time.

Moiré superlattices can induce correlated-electronic phases in twisted van der Waals materials: strongly correlated quantum phenomena emerge, such as superconductivity and the Mott-insulating state. However, moiré superlattices produced through artificial stacking can be quite inhomogeneous, which hampers the development of a clear correlation between the moiré period and the emerging electrical and optical properties. Here, it is demonstrated in twisted-bilayer transition-metal dichalcogenides that low-frequency Raman scattering can be utilized not only to detect atomic reconstruction, but also to map out the inhomogeneity of the moiré lattice over large areas. The method is established based on the finding that both the interlayer-breathing mode and moiré phonons are highly susceptible to the moiré period and provide characteristic fingerprints. Hyperspectral Raman imaging visualizes microscopic domains of a 5° twisted-bilayer sample with an effective twist-angle resolution of about 0.1°. This ambient methodology can be conveniently implemented to characterize and preselect high-quality areas of samples for subsequent device fabrication, and for transport and optical experiments.

Heterostructures of atomically thin van der Waals bonded monolayers have opened a unique platform to engineer Coulomb correlations, shaping excitonic, Mott insulating, or superconducting phases. In transition metal dichalcogenide heterostructures, electrons and holes residing in different monolayers can bind into spatially indirect excitons with a strong potential for optoelectronics, valleytronics, Bose condensation, superfluidity, and moir\'e-induced nanodot lattices. Yet these ideas require a microscopic understanding of the formation, dissociation, and thermalization dynamics of correlations including ultrafast phase transitions. Here we introduce a direct ultrafast access to Coulomb correlations between monolayers; phase-locked mid-infrared pulses allow us to measure the binding energy of interlayer excitons in WSe2/WS2 hetero-bilayers by revealing a novel 1s-2p resonance, explained by a fully quantum mechanical model. Furthermore, we trace, with subcycle time resolution, the transformation of an exciton gas photogenerated in the WSe2 layer directly into interlayer excitons. Depending on the stacking angle, intra- and interlayer species coexist on picosecond scales and the 1s-2p resonance becomes renormalized. Our work provides a direct measurement of the binding energy of interlayer excitons and opens the possibility to trace and control correlations in novel artificial materials., Comment: This is a post-peer-review, pre-copyedit version of an article published in Nature Materials. The final authenticated version is available online at https://doi.org/10.1038/s41563-019-0337-0

We report the observation of the undocumented visible one-photon photoluminescence (PL) of single silver nanorods excited by 532 and 633 nm continuous wave lasers with single-nanoparticle spectroscopy. We attribute the PL of silver nanorods to the intraband transition excited hot-electron radiative decay. The PL of silver nanorods closely resembles the corresponding LSPR scattering spectrum, and both are dependent on their aspect ratio. The good correlation between the quantitative PL intensity and the absorption cross section at the excitation wavelength of each nanorod leads to an aspect ratio independent PL quantum yield. The PL quantum yield of silver nanorods is similar to that of gold nanorods (10–6), indicating an efficient intraband excitation of hot electrons. The understanding of the PL mechanism of Ag nanorods points to the high-energy nature of the hot electrons excited via intraband transition, which has important indications in utilizing hot electrons for energy harvesting and photocatalysis.

Surface-enhanced Raman spectroscopy (SERS) has attracted tremendous interest as a label-free highly sensitive analytical method. For optimization of SERS activity, it is highly important to systematically investigate the size effect of nanoparticles on the SERS enhancement, which appears to be challenging in experiment, as the localized surface plasmon resonance (LSPR) of nanoparticles also changes with the change of the particle size. This challenge can be overcome by utilizing the unique property of gold nanorods, whose LSPR wavelength can be controlled to be the same by properly choosing the size and aspect ratio of the nanorods. We obtained the correlated SEM images, scattering spectra, and SERS spectra on a home-built single nanoparticle spectroscopy system and systematically investigate the size effect on SERS of individual gold nanorods using the adsorbed malachite green isothiocyanate (MGITC) molecule as the probe molecule. The dark field scattering intensity was found to increase with the increas...

Surface-enhanced Raman scattering (SERS) spectroscopy has attracted tremendous interests as a highly sensitive label-free tool. The local field produced by the excitation of localized surface plasmon resonances (LSPRs) dominates the overall enhancement of SERS. Such an electromagnetic enhancement is unfortunately accompanied by a strong modification in the relative intensity of the original Raman spectra, which highly distorts spectral features providing chemical information. Here we propose a robust method to retrieve the fingerprint of intrinsic chemical information from the SERS spectra. The method is established based on the finding that the SERS background originates from the LSPR-modulated photoluminescence, which contains the local field information shared also by SERS. We validate this concept of retrieval of intrinsic fingerprint information in well controlled single metallic nanoantennas of varying aspect ratios. We further demonstrate its unambiguity and generality in more complicated systems of tip-enhanced Raman spectroscopy (TERS) and SERS of silver nanoaggregates., We acknowledge support from NSFC (21633005, 21621091 and J1310024), MOST (2013CB933703 and 2016YFA0200601), MOE (IRT13036), and MINECO (FIS2016-80174-P) and Basque Government grant of UPV/EHU Grupos Consolidados IT-756-13. R.E. also acknowledges Fellow Gipuzkoa of the Gipuzkoako Foru Aldundia through the European Union’s FEDER program ‘Una manera de hacer Europa’.

Wide applications of surface plasmon resonance rely on the in-depth understanding of the near-field distribution over a metallic nanostructure. However, precisely locating the strongest electric field in a metallic nanostructure still remains a great challenge in experiments because the field strength decays exponentially from the surface. Here, we demonstrate that the hot spot position for gold nanoparticles over a metal film can be precisely located using surface-enhanced Raman spectroscopy (SERS) by rationally choosing the probe molecules and excitation wavelengths. The finite difference time domain simulation verifies the experimental results and further reveals that the enhancement for the above system is sensitive to the distance between nanoparticles and the metal film but insensitive to the distance of nanoparticles. On the basis of this finding, we propose and demonstrate an approach of using a nanoparticles-on-metal film substrate as a uniform SERS substrate. This work provides a convenient way to probe the location of strong near-field enhancement with SERS and will have important implications in both surface analysis and surface plasmonics.

Vladimir Bochenkov, Jeremy Baumberg, Mikhail Noginov, Felix Benz, Hasan Aldewachi, Silvan Schmid, Viktor Podolskiy, Javier Aizpurua, Kaiqiang Lin, Thomas Ebbesen, Alexei A Kornyshev, James Hutchison, Katarzyna Matczyszyn, Samir Kumar, Bart de Nijs, Francisco Rodŕiguez Fortuno, James T. Hugall, Pablo de Roque, Niek van Hulst, Santhosh Kotni, Olivier Martin, F. Javier Garcia de Abajo, Michael Flatte, Andrew Mount, Martin Moskovits, Pavel Ginzburg, David Zueco, Anatoly Zayats, Sang-Hyun Oh, Yu Chen, David Richards, Alessandro Belardini and Prineha Narang

Noble metal nanoparticles have unique localized surface plasmon resonance (LSPR), leading to their strong absorption and scattering in the visible light range. Up to date, the common practice in the selection of nanoparticles for a specific application is still based on the measured extinction spectra. This practice may be erroneous, because the extinction spectra contain both absorption and scattering contribution that may play different roles in different applications. It would be highly desirable to develop an efficient way to obtain the absorption and scattering spectra simultaneously. Herein, we develop a method to use the experimentally measured extinction and scattering signals to extract the absorption and scattering spectra that is in excellent agreement with that simulated by discrete dipole approximation (DDA). The heating curve measurement on the three types of gold nanorods, with almost the same extinction spectra but different absorption and scattering contribution, convincingly reveals an excellent correlation between the heating effect and the absorption strength rather than the extinction strength. The result demonstrates the importance to obtain the scattering and absorption spectra to predict the potential application for different types of nanoparticles, which in turn will screen efficiently nanoparticles for a specific application.

A facile method has been developed for face-to-face assembly of two-dimensional surfactant-free Pd nanosheets into one-dimensional Pd superlattice nanowires. The length of the Pd nanowires can be well controlled by introducing cations of different concentration and charge density. Our studies reveal that cations with higher charge density have stronger charge-screening ability, and their introduction leads to more positive zeta-potential and decreased electrostatic repulsion between negatively charged Pd nanosheets. Moreover, their surfactant-free feature is of great importance in assembling the Pd nanosheets into superlattice nanowires. While the cations are important for the assembly of Pd nanosheets, the use of poly(vinylpyrrolidone) is necessary to enhance the stability of the assembled superlattice nanowires. The as-assembled segmented Pd nanowires display tunable surface plasmon resonance features and excellent hydrogen-sensing properties.

Carbon monoxide can adsorb specifically on Pd(111) to induce the formation of unique Pd nanostructures. In the copresence of CO and H(2), single-crystalline Pd tetrapod nanocrystals have now been successfully prepared. The Pd tetrapods are enclosed by (111) surfaces and are yielded through hydride formation. Density functional theory calculations revealed that the formation of PdH(x) in the presence of H(2) reduces the binding energy of CO on Pd and thus helps to decrease the CO coverage during the synthesis, which is essential to the formation of the PdH(x) tetrapod nanocrystals. In addition to tetrapod nanocrystals, tetrahedral nanocrystals were also produced in the copresence of CO and H(2) when the reaction temperature was ramped to further lower the CO coverage. Upon aging in air, the as-prepared PdH(x) nanocrystals exhibited a shape-dependent hydrogen releasing behavior. The conversion rate of PdH(x) tetrapod nanocrystals into metallic Pd was faster than that of tetrahedral nanocrystals.