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Transition metal dichalcogenides (TMDs) are layered two-dimensional semiconductors explored for various optoelectronic applications, ranging from light-emitting diodes to single-photon emitters. To interact strongly with light, such devices require monolayer TMDs, which exhibit a direct bandgap. These atomically thin sheets are typically obtained through mechanical exfoliation followed by manual identification with a brightfield optical microscope. While this traditional procedure provides high-quality crystals, the identification step is time-intensive, low-throughput, and prone to human error, creating a significant bottleneck for TMD research. Here, we report a simple and fully automated approach for high-throughput identification of TMD monolayers using photoluminescence microscopy. Compared to a manual search and verification, our methodology offers a four-orders-of-magnitude decrease in the time a researcher must invest per identified monolayer. This ability enables us to measure geometric and photoluminescence-intensity features of more than 2,400 monolayers and bilayers of WSe$_2$, MoSe$_2$, and MoS$_2$. Due to these large numbers, we can study and quantify material properties previously inaccessible. For example, we show that the mean photoluminescence intensity from a monolayer correlates with its size due to reduced emission from its edges. Further, we observe large variations in brightness (up to 10$\times$) from WSe$_2$ monolayers of different batches produced by the same supplier. Therefore, our automated approach not only increases fabrication efficiency but also enhances sample quality for optoelectronic devices of atomically thin semiconductors.

Chemical syntheses that provide nanocrystals (NCs) with narrow distributions in size and shape are critical for NC research. This has led to the investigation of magic-sized NCs (MSNCs), a class of semiconductor crystallites that grow in discrete steps, potentially offering a single size and shape (i.e., monodispersity). However, the photoluminescence (PL) spectra of CdSe MSNCs measured at room temperature have been reported to be broader than those of state-of-the-art quantum dots. This difference could be due to the smaller size of MSNCs, which broadens their line widths, or due to their residual size dispersity. To better understand the optical performance of MSNCs, here we perform single-particle spectroscopy. Our results show that, while CdSe MSNCs do exhibit particle-to-particle variations that lead to modest broadening of their ensemble emission spectra, the largest contribution comes from the single-particle line width. By examining MSNCs with different sizes and shells, we conclude that this single-particle broadening is consistent with exciton coupling to acoustic phonons from the NC surface. Because of their small size, this coupling and the role of residual size dispersity have a larger impact on the ensemble emission line widths. Notably, when small (<2.7 nm diameter) MSNCs and quantum dots are compared, the ensemble PL line widths of MSNCs are actually sharper. Due to their small size, MSNCs also exhibit strong anti-bunching $[g^{(2)}(0) \sim 0.05]$ at room temperature. Thus, MSNCs represent a bright, spectrally pure class of quantum emitter, useful for applications in optoelectronic and quantum-information technologies where strong three-dimensional confinement is required.

Quantum dots are semiconductor nano-structures where particle motion is confined in all three spatial dimensions. Since their first experimental realization, nanocrystals confining the quanta of polarization waves, termed excitons, have found numerous applications in fields ranging from single photon sources for quantum information processing to commercial displays. A major limitation to further extending the range of potential applications has been the large inhomogeneity in, and lack-of tunability of, exciton energy that is generic to quantum dot materials. Here, we address this challenge by demonstrating electrically-defined quantum dots for excitons in monolayer semiconductors where the discrete exciton energies can be tuned using applied gate voltages. Resonance fluorescence measurements show strong spectral jumps and blinking of these resonances, verifying their zero-dimensional nature. Our work paves the way for realizing quantum confined bosonic modes where nonlinear response would arise exclusively from exciton--exciton interactions., Comment: updated version

While nanoscale semiconductor crystallites provide versatile fluorescent materials for light-emitting devices, such nanocrystals suffer from the "dark exciton"$\unicode{x2014}$an optically inactive electronic state into which the nanocrystal relaxes before emitting. Recently, a theoretical mechanism was discovered that can potentially defeat the dark exciton. The Rashba effect can invert the order of the lowest-lying levels, creating a bright excitonic ground state. To identify materials that exhibit this behavior, here we perform an extensive high-throughput computational search of two large open-source materials databases. Based on a detailed understanding of the Rashba mechanism, we define proxy criteria and screen over 500,000 solids, generating 173 potential "bright-exciton" materials. We then refine this list with higher-level first-principles calculations to obtain 28 candidates. To confirm the potential of these compounds, we select five and develop detailed effective-mass models to determine the nature of their lowest-energy excitonic state. We find that four of the five solids (BiTeCl, BiTeI, Ga$_2$Te$_3$, and KIO$_3$) can yield bright ground-state excitons. Our approach thus reveals promising materials for future experimental investigation of bright-exciton nanocrystals., Comment: 19 pages, 4 figures

Hexagonal boron nitride (hBN)-long-known as a thermally stable ceramic-is now available as atomically smooth, single-crystalline flakes, revolutionizing its use in optoelectronics. For nanophotonics, these flakes offer strong nonlinearities, hyperbolic dispersion, and single-photon emission, providing unique properties for optical and quantum-optical applications. For nanoelectronics, their pristine surfaces, chemical stability, and wide bandgap have made them the key substrate, encapsulant, and gate dielectric for two-dimensional electronic devices. However, while exploring these advantages, researchers have been restricted to flat flakes or those patterned with basic slits and holes, severely limiting advanced architectures. If freely varying flake profiles were possible, the hBN structure would present a powerful design parameter to further manipulate the flow of photons, electrons, and excitons in next-generation devices. Here, we demonstrate freeform nanostructuring of hBN by combining thermal scanning-probe lithography and reactive-ion etching to shape flakes with surprising fidelity. We leverage sub-nanometer height control and high spatial resolution to produce previously unattainable flake structures for a broad range of optoelectronic applications. For photonics, we fabricate microelements and show the straightforward transfer and integration of such elements by placing a spherical hBN microlens between two planar mirrors to obtain a stable, high-quality optical microcavity. We then decrease the patterning length scale to introduce Fourier surfaces for electrons, creating sophisticated, high-resolution landscapes in hBN, offering new possibilities for strain and band-structure engineering. These capabilities can advance the discovery and exploitation of emerging phenomena in hyperbolic metamaterials, polaritonics, twistronics, quantum materials, and 2D optoelectronic devices.

Quantum confinement is the discretization of energy when motion of particles is restricted to length scales smaller than their de Broglie wavelength. The experimental realization of this effect has had wide ranging impact in diverse fields of physics and facilitated the development of new technologies. In semiconductor physics, quantum confinement of optically excited quasiparticles, such as excitons or trions, is typically achieved by modulation of material properties - an approach crucially limited by the lack of insitu tunability and scalability of confining potentials. Achieving fully tunable quantum confinement of optical excitations has therefore been an outstanding goal in quantum photonics. Here, we demonstrate electrically controlled quantum confinement of neutral excitons in a gate-defined monolayer p-i-n diode. A combination of dc Stark shift induced by large in-plane fields and a previously unknown confining mechanism based on repulsive interaction between excitons and free charges ensures tight exciton confinement in the narrow neutral region. Quantization of exciton motion manifests in multiple discrete, spectrally narrow, voltage-dependent optical resonances that emerge below the free exciton resonance. Our measurements reveal several unique physical features of these quantum confined excitons, including an in-plane dipolar character, one-dimensional center-of-mass confinement, and strikingly enhanced exciton size in the presence of magnetic fields. Our method provides an experimental route towards creating scalable arrays of identical single photon sources, which will constitute building blocks of strongly correlated photonic systems.

Because surface plasmons can be confined below the diffraction limit, metallic lasers that support plasmonic modes can provide miniaturized sources of electromagnetic waves. Such devices often exploit a multilayer design, in which a semiconductor gain layer is placed near a metallic interface with a gap layer in between. However, despite many experimental demonstrations, key considerations for these planar metallic lasers remain understudied, leading to incorrect conclusions about the optimal design. Here, we pursue a detailed experimental and theoretical study of planar metallic lasers to explore the effect of design parameters on the lasing behavior. We print semiconductor nanoplatelets as a gain layer of controllable thickness onto alumina-coated silver films with integrated planar Fabry-P\'erot cavities. Lasing behavior is then monitored with spectrally and polarization-resolved far-field imaging. The results are compared with a theoretical waveguide model and a detailed rate-equation model, which consider both plasmonic and photonic modes. We show that the nature of the lasing mode is dictated by the gain-layer thickness. Moreover, by explicitly treating gain in our waveguide model, we find that, contrary to conventional wisdom, a gap layer with high refractive index is advantageous for plasmonic lasing. Additionally, our rate-equation model reveals a regime where plasmonic and photonic modes compete within the same device, raising the possibility of facile, active mode switching. These findings provide guidance for future designs of metallic lasers and could lead to on-chip lasers with controlled photonic and plasmonic output, switchable at high speeds., Comment: 51 pages, 14 figures (main text and supporting information merged)

Germanium telluride (GeTe), a phase-change material, is known to exhibit four different structural phases: three at room temperature (one amorphous and two crystalline, $\alpha$ and $\gamma$) and one at high temperature (crystalline $\beta$). Because transitions between the amorphous and crystalline phases lead to significant changes in material properties (e.g., refractive index and resistivity), GeTe has been investigated as a phase-change material for photonics, thermoelectrics, ferroelectrics, and spintronics. Consequently, the temperature-dependent phase transitions in GeTe have been studied for bulk and thin-film GeTe, both fabricated by sputtering. Colloidal synthesis of nanoparticles offers a more flexible fabrication approach for amorphous and crystalline GeTe. These nanoparticles are known to exhibit size-dependent properties, such as an increased crystallization temperature for the amorphous-to-$\alpha$ transition in sub-10\,nm GeTe particles. The $\alpha$-to-$\beta$ phase transition is also expected to vary with size, but this effect has not yet been investigated for GeTe. Here, we report time-resolved X-ray diffraction of GeTe nanoparticles with different diameters and from different synthetic protocols. We observe a non-volatile amorphous-to-$\alpha$ transition between 210$^{\circ}$C and 240$^{\circ}$C and a volatile $\alpha$-to-$\beta$ transition between 370$^{\circ}$C and 420$^{\circ}$C. The latter transition was reversible and repeatable. While the transition temperatures are shifted relative to the values known for bulk GeTe, the nanoparticle-based samples still exhibit the same structural phases reported for sputtered GeTe. Thus, colloidal GeTe maintains the same general phase behavior as bulk GeTe while allowing for more flexible and accessible fabrication. Therefore, nanoparticle-based GeTe films show great potential for applications, such as in active photonics.

Metasurfaces allow for the spatiotemporal variation of amplitude, phase, and polarization of optical wavefronts. Implementation of active tunability of metasurfaces promises compact flat optics capable of reconfigurable wavefront shaping. Phase-change materials (PCMs), such as germanium telluride or germanium antimony telluride, are a prominent material class enabling reconfigurable metasurfaces due to their large refractive index change upon structural transition. However, commonly employed laser-induced switching of PCMs limits the achievable feature sizes and thus, restricts device miniaturization. Here, we propose thermal scanning-probe-induced local switching of germanium telluride to realize near-infrared metasurfaces with feature sizes far below what is achievable with diffraction-limited optical switching. Our design is based on a planar multilayer stack and does not require fabrication of protruding dielectric or metallic resonators as commonly applied in the literature. Instead, we numerically demonstrate that a broad-band tuning of perfect absorption could be realized by the localized and controlled tip-induced crystallization of the PCM layer. The spectral response of the metasurface is explained using simple resonance mode analysis and numerical simulations. To facilitate experimental realization, we provide a detailed theoretical description of the tip-induced crystallization employing multiphysics simulations to demonstrate the great potential for fabricating compact reconfigurable metasurfaces. Our concept allows for tunable perfect absorption and can be applied not only for thermal imaging or sensing, but also for spatial frequency filtering., Comment: 7 pages, 4 figures

Phase-change materials (PCMs), which are well-established in optical and random-access memories, are increasingly studied for emerging topics such as brain-inspired computing and active photonics. These applications take advantage of the pronounced reflectivity and resistivity changes that accompany the structural transition in PCMs from their amorphous to crystalline state. However, PCMs are typically fabricated as thin films via sputtering, which is costly, requires advanced equipment, and limits the sample and device design. Here, we investigate a simpler and more flexi-ble approach for applications in tunable photonics: the use of sub-10 nm colloidal PCM nanoparticles (NPs). We report the optical properties of amorphous and crystalline germanium telluride (GeTe) NP thin films from the infrared to the ultraviolet spectral range. Using spectroscopic ellipsometry with support from cross-sectional scanning electron microscopy, atomic force microscopy, and absorption spectroscopy, we extract refractive indices n, extinction coefficients k, and band gaps Eg and compare to values known for sputtered GeTe thin films. We find a decrease of n and k and an increase of Eg for NP-based GeTe films, yielding insights into size-dependent property changes for nanoscale PCMs. Furthermore, our results reveal the suitability of GeTe NPs for tunable photonics in the near-infrared and visible spectral range. Finally, we studied sample reproducibility and aging of our NP films. We found that the colloidally-prepared PCM thin films were stable for at least two months stored under nitrogen, further supporting the great promise of these materials in applications., Comment: Optical Materials Engineering Laboratory, ETH Zurich, 8092 Zurich, Switzerland. IBM Research-Zurich, R\"uschlikon, Switzerland. Materials and Device Engineering Group, Department of Information Technology and Electrical Engineering, ETH Zurich, 8092 Zurich, Switzerland

Arrays of metallic particles patterned on a substrate have emerged as a promising design for on-chip plasmonic lasers. In past examples of such devices, the periodic particles provided feedback at a single resonance wavelength, and organic dye molecules were used as the gain material. Here, we introduce a flexible template-based fabrication method that allows a broader design space for Ag particle-array lasers. Instead of dye molecules, we integrate colloidal quantum dots (QDs), which offer better photostability and wavelength tunability. Our fabrication approach also allows us to easily adjust the refractive index of the substrate and the QD-film thickness. Exploiting these capabilities, we demonstrate not only single-wavelength lasing but dual-wavelength lasing via two distinct strategies. First, by using particle arrays with rectangular lattice symmetries, we obtain feedback from two orthogonal directions. The two output wavelengths from this laser can be selected individually using a linear polarizer. Second, by adjusting the QD-film thickness, we use higher-order transverse waveguide modes in the QD film to obtain dual-wavelength lasing at normal and off-normal angles from a symmetric square array. We thus show that our approach offers various design possibilities to tune the laser output.

Gratings and holograms are patterned surfaces that tailor optical signals by diffraction. Despite their long history, variants with remarkable functionalities continue to be discovered. Further advances could exploit Fourier optics, which specifies the surface pattern that generates a desired diffracted output through its Fourier transform. To shape the optical wavefront, the ideal surface profile should contain a precise sum of sinusoidal waves, each with a well-defined amplitude, spatial frequency, and phase. However, because fabrication techniques typically yield profiles with at most a few depth levels, complex 'wavy' surfaces cannot be obtained, limiting the straightforward mathematical design and implementation of sophisticated diffractive optics. Here we present a simple yet powerful approach to eliminate this design-fabrication mismatch by demonstrating optical surfaces that contain an arbitrary number of specified sinusoids. We combine thermal scanning-probe lithography and templating to create periodic and aperiodic surface patterns with continuous depth control and sub-wavelength spatial resolution. Multicomponent linear gratings allow precise manipulation of electromagnetic signals through Fourier-spectrum engineering. Consequently, we immediately resolve an important problem in photonics by creating a single-layer grating that simultaneously couples red, green, and blue light at the same angle of incidence. More broadly, we analytically design and accurately replicate intricate two-dimensional moir\'e patterns, quasicrystals, and holograms, demonstrating a variety of previously impossible diffractive surfaces. Therefore, this approach provides instant benefit for optical devices (biosensors, lasers, metasurfaces, and modulators) and emerging topics in photonics (topological structures, transformation optics, and valleytronics).

We optically trap freestanding single metallic chiral nanoparticles using a standing-wave optical tweezer. We also incorporate within the trap a polarimetric setup that allows to perform in situ chiral recognition of single enantiomers. This is done by measuring the S_3 component of the Stokes vector of a light beam scattered off the trapped nanoparticle in the forward direction. This unique combination of optical trapping and chiral recognition, all implemented within a single setup, opens new perspectives towards the control, recognition, and manipulation of chiral objects at nanometer scales., Comment: 8 pages, including Supplemental Material, 7 figures

Nanostructured semiconductors emit light from electronic states known as excitons[1]. According to Hund's rules[2], the lowest energy exciton in organic materials should be a poorly emitting triplet state. Analogously, the lowest exciton level in all known inorganic semiconductors is believed to be optically inactive. These 'dark' excitons (into which the system can relax) hinder light-emitting devices based on semiconductor nanostructures. While strategies to diminish their influence have been developed[3-5], no materials have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in quasi-cubic lead halide perovskites is optically active. We first use the effective-mass model and group theory to explore this possibility, which can occur when the strong spin-orbit coupling in the perovskite conduction band is combined with the Rashba effect [6-10]. We then apply our model to CsPbX3 (X=Cl,Br,I) nanocrystals[11], for which we measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright character of the lowest exciton immediately explains the anomalous photon-emission rates of these materials, which emit 20 and 1,000 times faster[12] than any other semiconductor nanocrystal at room[13-16] and cryogenic[17] temperatures, respectively. The bright exciton is further confirmed by detailed analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals[18], which are already used in lighting[19,20], lasers[21,22], and displays[23], these optically active excitons can lead to materials with brighter emission and enhanced absorption. More generally, our results provide criteria for identifying other semiconductors exhibiting bright excitons with potentially broad implications for optoelectronic devices., Comment: 14 pages and 3 figures in the main text, Methods and extended data 16 pages which include 11 figures, and supporting information 28 pages

Colloidal quantum dots are robust, efficient, and tunable emitters now used in lighting, displays, and lasers. Consequently, when the spaser, a laser-like source of surface plasmons, was first proposed, quantum dots were specified as the ideal plasmonic gain medium. Subsequent spaser designs, however, have required a single material to simultaneously provide gain and define the plasmonic cavity, an approach ill-suited to quantum dots and other colloidal nanomaterials. Here we develop a more open architecture that decouples the gain medium from the cavity, leading to a versatile class of quantum-dot-based spasers that allow controlled generation, extraction, and manipulation of plasmons. We first create high-quality-factor, aberration-corrected, Ag plasmonic cavities. We then incorporate quantum dots via electrohydrodynamic printing18,19 or drop-casting. Photoexcitation under ambient conditions generates monochromatic plasmons above threshold. This signal is extracted, directed through an integrated amplifier, and focused at a nearby nanoscale tip, generating intense electromagnetic fields. This spaser platform, deployable at different wavelengths, size scales, and geometries, can enable more complex on-chip plasmonic devices.

We report on a template-stripping method for the direct surface patterning of colloidal quantum-dot thin films to produce highly luminescent structures with feature sizes less than 100 nm. Through the careful design of high quality bulls-eye gratings we can produce strong directional beaming (10{\deg} divergence) with up to six-fold out-coupling enhancement of spontaneous emission in the surface-normal direction. A transition to narrow single-mode lasing is observed in these same structures at thresholds as low as 120 {\mu}J/cm2. Furthermore, making use of the size-tunable character of colloidal quantum dots, we demonstrate spectrally selective out-coupling of light from mixed quantum-dot films. Our results provide a straightforward route towards significantly improved optical properties of colloidal quantum-dot assemblies., Comment: preprint, 32 pages, 7 figures

Advancing open atmosphere printing technologies to produce features in the nanoscale range has important and broad applications ranging from electronics, to photonics, plasmonics and biology. Recently an electrohydrodynamic printing regime has been demonstrated in a rapid dripping mode (termed NanoDrip), where the ejected colloidal droplets from nozzles of diameters of O(1 {\mu}m) can controllably reach sizes an order of magnitude smaller than the nozzle and can generate planar and out-of-plane structures of similar sizes. Despite demonstrated capabilities, our fundamental understanding of important aspects of the physics of NanoDrip printing needs further improvement. Here we address the topics of charge content and transport in NanoDrip printing. We employ quantum dot and gold nanoparticle dispersions in combination with a specially designed, auxiliary, asymmetric electric field, targeting the understanding of charge locality (particles vs. solvent) and particle distribution in the deposits as indicated by the dried nanoparticle patterns (footprints) on the substrate. We show that droplets of alternating charge can be spatially separated when applying an ac field to the nozzle. The nanoparticles within a droplet are distributed asymmetrically under the influence of the auxiliary lateral electric field, indicating that they are the main carriers. We also show that the ligand length of the nanoparticles in the colloid affects their mobility after deposition (in the sessile droplet state).

Color printing at the diffraction limit has been recently explored by fabricating nanoscale plasmonic structures with electron beam lithography. However, only a limited color range and constant intensity throughout the structure have been demonstrated. Here we show an alternative, facile approach relying on the direct, open-atmosphere electrohydrodynamic rapid nanodrip printing of controlled amounts of red, green and blue (RGB) quantum dots at a resolution of 250 nm. The narrow emission spectrum of the dots allows the coverage of a very broad color space, exceeding standard RGB (sRGB) of modern display devices. We print color gradients of variable intensity, which to date could not be achieved with diffraction-limited resolution. Showcasing the capabilities of the technology, we present a photo-realistic printed image of a colorful parrot with a pixel size of 250 nm.

The fabrication of functional metamaterials with extreme feature resolution finds a host of applications such as the broad area of surface/light interaction. Non-planar features of such structures can significantly enhance their performance and tunability, but their facile generation remains a challenge. Here, we show that carefully designed out-of-plane nanopillars made of metal-dielectric composites integrated in a metal-dielectric-nanocomposite configuration, can absorb broadband light very effectively. We further demonstrate that electrohydrodynamic printing in a rapid nanodripping mode, is able to generate precise out-of-plane forests of such composite nanopillars with deposition resolutions at the diffraction limit on flat and non-flat substrates. The nanocomposite nature of the printed material allows the fine-tuning of the overall visible light absorption from complete absorption to complete reflection by simply tuning the pillar height. Almost perfect absorption (~95%) over the entire visible spectrum is achieved by a nanopillar forest covering only 6% of the printed area. Adjusting the height of individual pillar groups by design, we demonstrate on-demand control of the gray scale of a micrograph with a spatial resolution of 400 nm. These results constitute a significant step forward in ultra-high resolution facile fabrication of out-of-plane nanostructures, important to a broad palette of light design applications. nanostructures, important to a broad palette of light design applications.

Colloidal nanoplatelets - quasi-two-dimensional sheets of semiconductor exhibiting efficient, spectrally pure fluorescence - form when liquid-phase syntheses of spherical quantum dots are modified. Despite intense interest in their properties, the mechanism behind their anisotropic shape and precise atomic-scale thickness remains unclear, and even counterintuitive when their crystal structure is isotropic. One commonly accepted explanation is that nanoclusters nucleate within molecular templates and then fuse. Here, we test this mechanism for zincblende nanoplatelets and show that they form instead due to an intrinsic instability in growth kinetics. We synthesize CdSe and CdS1-xSex nanoplatelets in template- and solvent-free isotropic melts containing only cadmium carboxylate and chalcogen, a finding incompatible with previous explanations. Our model, based on theoretical results showing enhanced growth on narrow surface facets, rationalizes nanoplatelet formation and experimental dependencies on temperature, time, and carboxylate length. Such understanding should lead to improved syntheses, controlled growth on surfaces, and broader libraries of nanoplatelet materials., Comment: 57 pages, 23 figures (main text and supporting information merged), submitted

High-quality materials are critical for advances in plasmonics, especially as researchers now investigate quantum effects at the limit of single surface plasmons or exploit ultraviolet- or CMOS-compatible metals such as aluminum or copper. Unfortunately, due to inexperience with deposition methods, many plasmonics researchers deposit metals under the wrong conditions, severely limiting performance unnecessarily. This is then compounded as others follow their published procedures. In this perspective, we describe simple rules collected from the surface-science literature that allow high-quality plasmonic films of aluminum, copper, gold, and silver to be easily deposited with commonly available equipment (a thermal evaporator). Recipes are also provided so that films with optimal optical properties can be routinely obtained., Comment: Optical Materials Engineering Laboratory, ETH Zurich, 8092 Zurich, Switzerland

To optimize the interaction between chiral matter and highly twisted light, quantities that can help characterize chiral electromagnetic fields near nanostructures are needed. Here, by analogy with Poynting's theorem, we formulate the time-averaged conservation law of optical chirality in lossy dispersive media and identify the optical chirality flux as an ideal far-field observable for characterizing chiral optical near fields. Bounded by the conservation law, we show that it provides precise information, unavailable from circular dichroism spectroscopy, on the magnitude and handedness of highly twisted fields near nanostructures., Comment: 10 pages, 7 figures

Although poorly understood, cation-exchange reactions are increasingly used to dope or transform colloidal semiconductor nanocrystals (quantum dots). We used density-functional theory and kinetic Monte Carlo simulations to develop a microscopic theory that explains structural, optical, and electronic changes observed experimentally in Ag-cation-exchanged CdSe nanocrystals. We find that Coulomb interactions, both between ionized impurities and with the polarized nanocrystal surface, play a key role in cation exchange. Our theory also resolves several experimental puzzles related to photoluminescence and electrical behavior in CdSe nanocrystals doped with Ag., Comment: 12 pages, 4 figures. Published in Physical Review Letters. Supplementary information is included as ancillary file. The movie can be downloaded from http://journals.aps.org/prl/abstract/10.1103/PhysRevLett.113.156803

We present ultrafast optical switching experiments on 3D photonic band gap crystals. Switching the Si inverse opal is achieved by optically exciting free carriers by a two-photon process. We probe reflectivity in the frequency range of second order Bragg diffraction where the photonic band gap is predicted. We find good experimental switching conditions for free-carrier plasma frequencies between 0.3 and 0.7 times the optical frequency: we thus observe a large frequency shift of up to D omega/omega= 1.5% of all spectral features including the peak that corresponds to the photonic band gap. We deduce a corresponding large refractive index change of Dn'_Si/n'_Si= 2.0% and an induced absorption length that is longer than the sample thickness. We observe a fast decay time of 21 ps, which implies that switching could potentially be repeated at GHz rates. Such a high switching rate is relevant to future switching and modulation applications.