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.

Orientation of Individual Anisotropic Nanocrystals Identified by Polarization Fingerprint.

The polarization of photoluminescence emitted from anisotropic nanocrystals directly reflects the symmetry of the eigenstates involved in the recombination process and can thus be considered as a characteristic feature of a nanocrystal. We performed polarization resolved magneto-photoluminescence spectroscopy on single colloidal Mn2+:CdSe/CdS core-shell quantum dots of wurtzite crystal symmetry. At zero magnetic field, a distinct linear polarization pattern is observed, while applying a magnetic field enforces circularly polarized emission with a characteristic saturation value below 100%. These polarization features are shown to act as a specific fingerprint of each individual nanocrystal. A model considering the orientation of the crystal c⃗ axis with respect to the optical axis and the magnetic field and taking into account the impact of magnetic doping is introduced and quantitatively explains our findings. We demonstrate that a careful analysis of the polarization state of single nanocrystal emission using the full set of Stokes parameters allows for identification of the complete three-dimensional orientation of the crystal anisotropy axis of an individual nanoobject in lab coordinates.

Giant band splittings in EuS and EuSe magnetic semiconductor nanocrystals.

Using magnetic circular dichroism (MCD) spectroscopy, we demonstrate giant temperature- and field-dependent conduction-band splittings in colloidal EuS and EuSe nanocrystals.

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.

A Selective Cation Exchange Strategy for the Synthesis of Colloidal Yb3+-Doped Chalcogenide Nanocrystals with Strong Broadband Visible Absorption and Long-Lived Near-Infrared Emission.

Doping lanthanide ions into colloidal semiconductor nanocrystals is a promising strategy for combining their sharp and efficient 4f-4f emission with the strong broadband absorption and low-phonon-energy crystalline environment of semiconductors to make new solution-processable spectral-conversion nanophosphors, but synthesis of this class of materials has proven extraordinarily challenging because of fundamental chemical incompatibilities between lanthanides and most intermediate-gap semiconductors. Here, we present a new strategy for accessing lanthanide-doped visible-light-absorbing semiconductor nanocrystals by demonstrating selective cation exchange to convert precursor Yb3+-doped NaInS2 nanocrystals into Yb3+-doped PbIn2S4 nanocrystals. Excitation spectra and time-resolved photoluminescence measurements confirm that Yb3+ is both incorporated within the PbIn2S4 nanocrystals and sensitized by visible-light photoexcitation of these nanocrystals. This combination of strong broadband visible absorption, sharp near-infrared emission, and long (>400 µs) emission lifetimes in a colloidal nanocrystal system opens promising new opportunities for both fundamental-science and next-generation spectral-conversion applications such as luminescent solar concentrators.

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.

Mid-Gap States and Normal vs Inverted Bonding in Luminescent Cu+- and Ag+-Doped CdSe Nanocrystals.

Mid-gap luminescence in copper (Cu+)-doped semiconductor nanocrystals (NCs) involves recombination of delocalized conduction-band electrons with copper-localized holes. Silver (Ag+)-doped semiconductor NCs show similar mid-gap luminescence at slightly (∼0.3 eV) higher energy, suggesting a similar luminescence mechanism, but this suggestion appears inconsistent with the large difference between Ag+ and Cu+ ionization energies (∼1.5 eV), which should make hole trapping by Ag+ highly unfavorable. Here, Ag+-doped CdSe NCs (Ag+:CdSe) are studied using time-resolved variable-temperature photoluminescence (PL) spectroscopy, magnetic circularly polarized luminescence (MCPL) spectroscopy, and time-dependent density functional theory (TD-DFT) to address this apparent paradox. In addition to confirming that Ag+:CdSe and Cu+:CdSe NCs display similar broad PL with large Stokes shifts, we demonstrate that both also show very similar temperature-dependent PL lifetimes and magneto-luminescence. Electronic-structure calculations further predict that both dopants generate similar localized mid-gap states. Despite these strong similarities, we conclude that these materials possess significantly different electronic structures. Specifically, whereas photogenerated holes in Cu+:CdSe NCs localize primarily in Cu(3d) orbitals, formally oxidizing Cu+ to Cu2+, in Ag+:CdSe NCs they localize primarily in 4p orbitals of the four neighboring Se2- ligands, and Ag+ is not oxidized. This difference reflects a shift from "normal" to "inverted" bonding going from Cu+ to Ag+. The spectroscopic similarities are explained by the fact that, in both materials, photogenerated holes are localized primarily within covalent [MSe4] dopant clusters (M = Ag+, Cu+). These findings reconcile the similar spectroscopies of Ag+- and Cu+-doped semiconductor NCs with the vastly different ionization potentials of their Ag+ and Cu+ dopants.

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.

Digital Doping in Magic-Sized CdSe Clusters.

Magic-sized semiconductor clusters represent an exciting class of materials located at the boundary between quantum dots and molecules. It is expected that replacing single atoms of the host crystal with individual dopants in a one-by-one fashion can lead to unique modifications of the material properties. Here, we demonstrate the dependence of the magneto-optical response of (CdSe)13 clusters on the discrete number of Mn(2+) ion dopants. Using time-of-flight mass spectrometry, we are able to distinguish undoped, monodoped, and bidoped cluster species, allowing for an extraction of the relative amount of each species for a specific average doping concentration. A giant magneto-optical response is observed up to room temperature with clear evidence that exclusively monodoped clusters are magneto-optically active, whereas the Mn(2+) ions in bidoped clusters couple antiferromagnetically and are magneto-optically passive. Mn(2+)-doped clusters therefore represent a system where magneto-optical functionality is caused by solitary dopants, which might be beneficial for future solotronic applications.

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.

Valence-band mixing effects in the upper-excited-state magneto-optical responses of colloidal Mn2+-doped CdSe quantum dots.

We present an experimental study of the magneto-optical activity of multiple excited excitonic states of manganese-doped CdSe quantum dots chemically prepared by the diffusion doping method. Giant excitonic Zeeman splittings of each of these excited states can be extracted for a series of quantum dot sizes and are found to depend on the radial quantum number of the hole envelope function involved in each transition. As seven out of eight transitions involve the same electron energy state, 1Se, the dominant hole character of each excitonic transition can be identified, making use of the fact that the g-factor of the pure heavy-hole component has a different sign compared to pure light hole or split-off components. Because the magnetic exchange interactions are sensitive to hole state mixing, the giant Zeeman splittings reported here provide clear experimental evidence of quantum-size-induced mixing among valence-band states in nanocrystals.

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.

Two-dimensional higher order noise spectroscopy up to radio frequencies.

Going beyond the usual determination of the frequency-resolved power spectrum of an electrical noise signal, we implement a setup for the determination of a frequency-resolved two-dimensional correlation spectrum. We demonstrate measurements of two-dimensional correlation spectra with sampling rates up to 180 MSamples/s and real-time numerical evaluation with up to 100% data coverage. As an example, the purely Gaussian behavior of 1/f resistor noise is demonstrated with unprecedented sensitivity by verifying the absence of correlations between different frequencies. Unlike the usual power spectrum, the correlation spectrum is shown to contain information on both the homogeneous and inhomogeneous linewidths of a signal, suggesting applications in spin noise spectroscopy and signal analysis in general.