Impact of synthesis temperature and precursor ratio on the crystal quality of MOCVD WSe2monolayers.

Structural defects in transition metal dichalcogenide (TMDC) monolayers (ML) play a significant role in determining their (opto)electronic properties, triggering numerous efforts to control defect densities during material growth or by post-growth treatments. Various types of TMDC have been successfully deposited by MOCVD (metal-organic chemical vapor deposition), which is a wafer-scale deposition technique with excellent uniformity and controllability. However, so far there are no findings on the extent to which the incorporation of defects can be controlled by growth parameters during MOCVD processes of TMDC. In this work, we investigate the effect of growth temperature and precursor ratio during MOCVD of tungsten diselenide (WSe2) on the growth of ML domains and their impact on the density of defects. The aim is to find parameter windows that enable the deposition of WSe2ML with high crystal quality, i.e. a low density of defects. Our findings confirm that the growth temperature has a large influence on the crystal quality of TMDC, significantly stronger than found for the W to Se precursor ratio. Raising the growth temperatures in the range of 688 °C to 791 °C leads to an increase of the number of defects, dominating photoluminescence (PL) at low temperatures (5.6 K). In contrast, an increase of the molar precursor ratio (DiPSe/WCO) from 1000 up to 100 000 leads to less defect-related PL at low temperatures.

Silver nanowire electrodes for transparent light emitting devices based on WS2monolayers.

Transition metal dichalcogenide (TMDC) monolayers with their direct band gap in the visible to near-infrared spectral range have emerged over the past years as highly promising semiconducting materials for optoelectronic applications. Progress in scalable fabrication methods for TMDCs like metal-organic chemical vapor deposition (MOCVD) and the ambition to exploit specific material properties, such as mechanical flexibility or high transparency, highlight the importance of suitable device concepts and processing techniques. In this work, we make use of the high transparency of TMDC monolayers to fabricate transparent light-emitting devices (LEDs). MOCVD-grown WS2is embedded as the active material in a scalable vertical device architecture and combined with a silver nanowire (AgNW) network as a transparent top electrode. The AgNW network was deposited onto the device by a spin-coating process, providing contacts with a sheet resistance below 10 Ω sq-1and a transmittance of nearly 80%. As an electron transport layer we employed a continuous 40 nm thick zinc oxide (ZnO) layer, which was grown by atmospheric pressure spatial atomic layer deposition (AP-SALD), a precise tool for scalable deposition of oxides with defined thickness. With this, LEDs with an average transmittance over 60% in the visible spectral range, emissive areas of several mm2and a turn-on voltage of around 3 V are obtained.

Spectral fingerprints of individual Mn2+ impurities and Mn2+ pairs in magic-sized nanoclusters.

The chemical synthesis of (CdSe)13 magic-sized clusters (MSCs) allows the replacement of host atoms by individual transition metals such as Mn. By analyzing the spectral fingerprints of the Mn2+ photoluminescence (PL) in MSCs with different dopant concentrations, we are able to distinguish between single Mn2+ ions and coupled Mn2+ pairs. In case of Mn2+ pair emission, temperature-dependent studies show a pronounced red shift, followed by a distinct blue shift of the PL energy upon heating. This is related to a spin ladder formation of the ground and excited states due to Mn2+-Mn2+ exchange interaction at cryogenic temperatures, which is assumed to vanish at higher temperatures. In contrast, single Mn2+ ion PL exhibits a unique redshift with increasing temperature, which can be attributed to a particularly strong coupling to vibronic modes due to the ultimate small size of the MSCs.

Temperature dependence of Fano resonances in CrPS4.

A Fano resonance, as often observed in scattering, absorption, or transmission experiments, arises from quantum interference between a discrete optical transition and a continuous background. Here, we present a temperature-dependent study on Fano resonances observed in photoluminescence from flakes of the layered semiconductor antiferromagnet chromium thiophosphate (CrPS4). Two Fano resonances with a distinctly different temperature dependence were identified. The continuous background that is responsible for the Fano resonances is attributed to the d-d transition of the optically active Cr3+ center, predominantly the spin-forbidden 2Eg → 4A2g transition with contributions of the broad-band 4T2g → 4A2g transition. The discrete states that interfere with this continuous background are suggested to arise from localized atomic phosphorus. A model idea for explaining the individual temperature dependence of the Fano resonances is presented.

Optical Probing of Crystal Lattice Configurations in Single CsPbBr3 Nanoplatelets.

Quantum-confined nanostructures of CsPbBr3 with luminescence quantum efficiencies approaching unity have shown tremendous potential for lighting and quantum light applications. In contrast to CsPbBr3 quantum dots, where the fine structure of the emissive exciton state has been intensely discussed, the relationship among lattice orientation, shape anisotropy, and exciton fine structure in lead halide nanoplatelets has not yet been established. In this work, we investigate the fine structure of the bright triplet exciton of individual CsPbBr3 nanoplatelets by polarization-resolved micro- and magnetophotoluminescence spectroscopy at liquid helium temperature and find a large zero-field splitting of up to 2.5 meV. A unique relation between the crystal structure and the photoluminescence emission confirms the existence of two distinct crystal configurations in such nanoplatelets with different alignments of the crystal axes with respect to the nanoplatelet facets. Polarization-resolved experiments eventually allow us to determine the absolute orientation of an individual nanoplatelet on the substrate purely by optical means.

Directed Exciton Magnetic Polaron Formation in a Single Colloidal Mn2+:CdSe/CdS Quantum Dot.

One of the most prominent signatures of transition-metal doping in colloidal nanocrystals is the formation of charge carrier-induced magnetization of the dopant spin sublattice, called exciton magnetic polaron (EMP). Understanding the direction of EMP formation, however, is still a major obstacle. Here, we present a series of temperature-dependent photoluminescence studies on single colloidal Mn2+:CdSe/CdS core/shell quantum dots (QDs) performed in a vector magnetic field providing a unique insight into the interaction between individual excitons and numerous magnetic impurities. The energy of the QD emission and its full width at half-maximum are controlled by the interplay of EMP formation and statistical magnetic fluctuations, in excellent agreement with theory. Most important, we give the first direct demonstration that anisotropy effects-hypothesized for more than a decade-dominate the direction of EMP formation. Our findings reveal a pathway for directing the orientation of optically induced magnetization in colloidal nanocrystals.

Impurity incorporation and exchange interactions in Co2+-doped CdSe/CdS core/shell nanoplatelets.

The intentional incorporation of transition metal impurities into colloidal semiconductor nanocrystals allows an extension of the host material's functionality. While dopant incorporation has been extensively investigated in zero-dimensional quantum dots, the substitutional replacement of atoms in two-dimensional (2D) nanostructures by magnetic dopants has been reported only recently. Here, we demonstrate the successful incorporation of Co2+ ions into the shell of CdSe/CdS core/shell nanoplatelets, using these ions (i) as microscopic probes for gaining distinct structural insights and (ii) to enhance the magneto-optical functionality of the host material. Analyzing interatomic Co2+ ligand field transitions, we conclude that Co2+ is incorporated into lattice sites of the CdS shell, and effects such as diffusion of dopants into the CdSe core or diffusion of the dopants out of the heterostructure causing self-purification play a minor role. Taking advantage of the absorption-based technique of magnetic circular dichroism, we directly prove the presence of sp-d exchange interactions between the dopants and the band charge carriers in CdSe/Co2+:CdS heteronanoplatelets. Thus, our study not only demonstrates magneto-optical functionality in 2D nanocrystals by Co2+ doping but also shows that a careful choice of the dopant type paves the way for a more detailed understanding of the impurity incorporation process into these novel 2D colloidal materials.

Phonon Interaction and Phase Transition in Single Formamidinium Lead Bromide Quantum Dots.

Formamidinium lead bromide (FAPbBr3) quantum dots (QDs) are promising materials for light emitting applications in the visible spectral region because of their high photoluminescence (PL) quantum yield (QY) and the enhanced chemical stability as compared to, for instance, methylammonium based analogues. Toward practical harnessing of their compelling optical characteristics, the exciton recombination process, and in particular the exciton-phonon interaction and the impact of crystal phase transition, has to be understood in detail. This is addressed in this contribution by PL studies on single colloidal FAPbBr3 QDs. Polarization-resolved PL measurements reveal a fine structure splitting of excitonic transitions due to the Rashba effect. Distinct phonon replica have been observed within energetic distances of 4.3 ± 0.5, 8.6 ± 0.9, and 13.2 ± 1.1 meV from the zero phonon line, which we attribute to vibrational modes of the lead bromide lattice. Additional vibrational modes of 18.6 ± 0.3 and 38.8 ± 1.1 meV are found and related to liberation modes of the formamidinium (FA) cation. Temperature-dependent PL spectra reveal a line broadening of the emission caused by exciton phonon interaction as well an unusual energy shift which is attributed to a crystal phase transition within the single QD.

sp-d Exchange Interactions in Wave Function Engineered Colloidal CdSe/Mn:CdS Hetero-Nanoplatelets.

In two-dimensional (2D) colloidal semiconductor nanoplatelets, which are atomically flat nanocrystals, the precise control of thickness and composition on the atomic scale allows for the synthesis of heterostructures with well-defined electron and hole wave function distributions. Introducing transition metal dopants with a monolayer precision enables tailored magnetic exchange interactions between dopants and band states. Here, we use the absorption based technique of magnetic circular dichroism (MCD) to directly prove the exchange coupling of magnetic dopants with the band charge carriers in hetero-nanoplatelets with CdSe core and manganese-doped CdS shell (CdSe/Mn:CdS). We show that the strength of both the electron as well as the hole exchange interactions with the dopants can be tuned by varying the nanoplatelets architecture with monolayer accuracy. As MCD is highly sensitive for excitonic resonances, excited level spectroscopy allows us to resolve and identify, in combination with wave function calculations, several excited state transitions including spin-orbit split-off excitonic contributions. Thus, our study not only demonstrates the possibility to expand the extraordinary physical properties of colloidal nanoplatelets toward magneto-optical functionality by transition metal doping but also provides an insight into the excited state electronic structure in this novel two-dimensional material.

Co2+-Doping of Magic-Sized CdSe Clusters: Structural Insights via Ligand Field Transitions.

Magic-sized clusters represent materials with unique properties at the border between molecules and solids and provide important insights into the nanocrystal formation process. However, synthesis, doping, and especially structural characterization become more and more challenging with decreasing cluster size. Herein, we report the successful introduction of Co2+ ions into extremely small-sized CdSe clusters with the intention of using internal ligand field transitions to obtain structural insights. Despite the huge mismatch between the radii of Cd2+ and Co2+ ions (>21%), CdSe clusters can be effectively synthesized with a high Co2+ doping concentration of ∼10%. Optical spectroscopy and mass spectrometry suggest that one or two Co2+ ions are substitutionally embedded into (CdSe)13 clusters, which is known as one of the smallest CdSe clusters. Using magnetic circular dichroism spectroscopy on the intrinsic ligand field transitions between the different 3d orbitals of the transition metal dopants, we demonstrate that the Co2+ dopants are embedded on pseudotetrahedral selenium coordinated sites despite the limited number of atoms in the clusters. A significant shortening of Co-Se bond lengths compared to bulk or nanocrystals is observed, which results in the metastability of Co2+ doping. Our results not only extend the doping chemistry of magic-sized semiconductor nanoclusters, but also suggest an effective method to characterize the local structure of these extremely small-sized clusters.

Current-Induced Magnetic Polarons in a Colloidal Quantum-Dot Device.

Electrical spin manipulation remains a central challenge for the realization of diverse spin-based information processing technologies. Motivated by the demonstration of confinement-enhanced sp-d exchange interactions in colloidal diluted magnetic semiconductor (DMS) quantum dots (QDs), such materials are considered promising candidates for future spintronic or spin-photonic applications. Despite intense research into DMS QDs, electrical control of their magnetic and magneto-optical properties remains a daunting goal. Here, we report the first demonstration of electrically induced magnetic polaron formation in any DMS, achieved by embedding Mn2+-doped CdSe/CdS core/shell QDs as the active layer in an electrical light-emitting device. Tracing the electroluminescence from cryogenic to room temperatures reveals an anomalous energy shift that reflects current-induced magnetization of the Mn2+ spin sublattice, that is, excitonic magnetic polaron formation. These electrically induced magnetic polarons exhibit an energy gain comparable to their optically excited counterparts, demonstrating that magnetic polaron formation is achievable by current injection in a solid-state device.

Chemical Synthesis, Doping, and Transformation of Magic-Sized Semiconductor Alloy Nanoclusters.

Nanoclusters are important prenucleation intermediates for colloidal nanocrystal synthesis. In addition, they exhibit many intriguing properties originating from their extremely small size lying between molecules and typical nanocrystals. However, synthetic control of multicomponent semiconductor nanoclusters remains a daunting goal. Here, we report on the synthesis, doping, and transformation of multielement magic-sized clusters, generating the smallest semiconductor alloys. We use Lewis acid-base reactions at room temperature to synthesize alloy clusters containing three or four types of atoms. Mass spectrometry reveals that the alloy clusters exhibit "magic-size" characteristics with chemical formula of ZnxCd13-xSe13 (x = 0-13) whose compositions are tunable between CdSe and ZnSe. Successful doping of these clusters creates a new class of diluted magnetic semiconductors in the extreme quantum confinement regime. Furthermore, the important role of these alloy clusters as prenucleation intermediates is demonstrated by low temperature transformation into quantum alloy nanoribbons and nanorods. Our study will facilitate the understanding of these novel diluted magnetic semiconductor nanoclusters, and offer new possibilities for the controlled synthesis of nanomaterials at the prenucleation stage, consequently producing novel multicomponent nanomaterials that are difficult to synthesize.

Giant Excitonic Exchange Splittings at Zero Field in Single Colloidal CdSe Quantum Dots Doped with Individual Mn2+ Impurities.

Replacing a single atom of a host semiconductor nanocrystal with a functional dopant can introduce completely new properties potentially valuable for "solotronic" information-processing applications. Here, we report successful doping of colloidal CdSe quantum dots with a very small number of manganese ions-down to the ultimate limit of one. Single-particle spectroscopy reveals spectral fingerprints of the spin-spin interactions between individual dopants and quantum-dot excitons. Spectrally well-resolved emission peaks are observed that can be related to the discrete spin projections of individual Mn2+ ions. In agreement with theoretical predictions, the exchange splittings are enhanced by more than an order of magnitude in these quantum dots compared to their epitaxial counterparts, opening a path for solotronic applications at elevated temperatures.

High-speed GaN/GaInN nanowire array light-emitting diode on silicon(111).

The high speed on-off performance of GaN-based light-emitting diodes (LEDs) grown in c-plane direction is limited by long carrier lifetimes caused by spontaneous and piezoelectric polarization. This work demonstrates that this limitation can be overcome by m-planar core-shell InGaN/GaN nanowire LEDs grown on Si(111). Time-resolved electroluminescence studies exhibit 90-10% rise- and fall-times of about 220 ps under GHz electrical excitation. The data underline the potential of these devices for optical data communication in polymer fibers and free space.

Route to the Smallest Doped Semiconductor: Mn(2+)-Doped (CdSe)13 Clusters.

Doping semiconductor nanocrystals with magnetic transition-metal ions has attracted fundamental interest to obtain a nanoscale dilute magnetic semiconductor, which has unique spin exchange interaction between magnetic spin and exciton. So far, the study on the doped semiconductor NCs has usually been conducted with NCs with larger than 2 nm because of synthetic challenges. Herein, we report the synthesis and characterization of Mn(2+)-doped (CdSe)13 clusters, the smallest doped semiconductors. In this study, single-sized doped clusters are produced in large scale. Despite their small size, these clusters have semiconductor band structure instead of that of molecules. Surprisingly, the clusters show multiple excitonic transitions with different magneto-optical activities, which can be attributed to the fine structure splitting. Magneto-optically active states exhibit giant Zeeman splittings up to elevated temperatures (128 K) with large g-factors of 81(±8) at 4 K. Our results present a new synthetic method for doped clusters and facilitate the understanding of doped semiconductor at the boundary of molecules and quantum nanostructure.

Graphene-Enhanced UV-C LEDs.

Light-emitting diodes in the UV-C spectral range (UV-C LEDs) can potentially replace bulky and toxic mercury lamps in a wide range of applications including sterilization and water purification. Several obstacles still limit the efficiencies of UV-C LEDs. Devices in flip-chip geometry suffer from a huge difference in the work functions between the p-AlGaN and high-reflective Al mirrors, whereas the absence of UV-C transparent current spreading layers limits the development of UV-C LEDs in standard geometry. Here it is demonstrated that transfer-free graphene implemented directly onto the p-AlGaN top layer by a plasma enhanced chemical vapor deposition approach enables highly efficient 275 nm UV-C LEDs in both, flip-chip and standard geometry. In flip-chip geometry, the graphene acts as a contact interlayer between the Al-mirror and the p-AlGaN enabling an external quantum efficiency (EQE) of 9.5% and a wall-plug efficiency (WPE) of 5.5% at 8 V. Graphene combined with a ≈1 nm NiOx support layer allows a turn-on voltage <5 V. In standard geometry graphene acts as a current spreading layer on a length scale up to 1 mm. These top-emitting devices exhibit a EQE of 2.1% at 8.7 V and a WPE of 1.1%.

Demystifying Trion Emission in CdSe Nanoplatelets.

At cryogenic temperatures, the photoluminescence spectrum of CdSe nanoplatelets (NPLs) usually consists of multiple emission lines, the origin of which is still under debate. While there seems to be consensus that both neutral excitons and trions contribute to the NPL emission, the prominent role of trions is rather puzzling. In this work, we demonstrate that Förster resonant energy transfer in stacks of NPLs combined with hole trap states in specific NPLs within the stack trigger trion formation, while single NPL spectra are dominated by neutral excitonic emission. This interpretation is verified by implementing copper (Cu+) dopants into the lattice as intentional hole traps. Trion emission gets strongly enhanced, and due to the large amount of hole trapping Cu+ states in each single NPL, trion formation does not necessarily require stacking of NPLs. Thus, the ratio between trion and neutral exciton emission can be controlled by either changing the amount of stacked NPLs during sample preparation or implementing copper dopants into the lattice which act as additional hole traps.

Quantum confinement-controlled exchange coupling in manganese(II)-doped CdSe two-dimensional quantum well nanoribbons.

The impact of quantum confinement on the exchange interaction between charge carriers and magnetic dopants in semiconductor nanomaterials has been controversially discussed for more than a decade. We developed manganese-doped CdSe quantum well nanoribbons with a strong quantum confinement perpendicular to the c-axis, showing distinct heavy hole and light hole resonances up to 300 K. This allows a separate study of the s-d and the p-d exchange interactions all the way up to room temperature. Taking into account the optical selection rules and the statistical distribution of the nanoribbons orientation on the substrate, a remarkable change in particular of the s-d exchange constant with respect to bulk is indicated. Room-temperature studies revealed an unusually high effective g-factor up to ~13 encouraging the implementation of the DMS quantum well nanoribbons for (room temperature) spintronic applications.