Charles J. Barrows

Nanocrystal diffusion doping.

A diffusion-based synthesis of doped colloidal semiconductor nanocrystals is demonstrated. This approach involves thermodynamically controlled addition of both impurity cations and host anions to preformed seed nanocrystals under equilibrium conditions, rather than kinetically controlled doping during growth. This chemistry allows thermodynamic crystal compositions to be prepared without sacrificing other kinetically trapped properties such as shape, size, or crystallographic phase. This doping chemistry thus shares some similarities with cation-exchange reactions, but proceeds without the loss of host cations and excels at the introduction of relatively unreactive impurity ions that have not been previously accessible using cation exchange. Specifically, we demonstrate the preparation of Cd(1-x)Mn(x)Se (0 ≤ x ≤ ∼0.2) nanocrystals with narrow size distribution, unprecedentedly high Mn(2+) content, and very large magneto-optical effects by diffusion of Mn(2+) into seed CdSe nanocrystals grown by hot injection. Controlling the solution and lattice chemical potentials of Cd(2+) and Mn(2+) allows Mn(2+) diffusion into the internal volumes of the CdSe nanocrystals with negligible Ostwald ripening, while retaining the crystallographic phase (wurtzite or zinc blende), shape anisotropy, and ensemble size uniformity of the seed nanocrystals. Experimental results for diffusion doping of other nanocrystals with other cations are also presented that indicate this method may be generalized, providing access to a variety of new doped semiconductor nanostructures not previously attainable by kinetic routes or cation exchange.

Tuning Equilibrium Compositions in Colloidal Cd1–xMnxSe Nanocrystals Using Diffusion Doping and Cation Exchange

The physical properties of semiconductor nanocrystals can be tuned dramatically via composition control. Here, we report a detailed investigation of the synthesis of high-quality colloidal Cd1-xMnxSe nanocrystals by diffusion doping of preformed CdSe nanocrystals. Until recently, Cd1-xMnxSe nanocrystals proved elusive because of kinetic incompatibilities between Mn(2+) and Cd(2+) chemistries. Diffusion doping allows Cd1-xMnxSe nanocrystals to be prepared under thermodynamic rather than kinetic control, allowing access to broader composition ranges. We now investigate this chemistry as a model system for understanding the characteristics of nanocrystal diffusion doping more deeply. From the present work, a Se(2-)-limited reaction regime is identified, in which Mn(2+) diffusion into CdSe nanocrystals is gated by added Se(2-), and equilibrium compositions are proportional to the amount of added Se(2-). At large added Se(2-) concentrations, a solubility-limited regime is also identified, in which x = xmax = ∼0.31, independent of the amount of added Se(2-). We further demonstrate that Mn(2+) in-diffusion can be reversed by cation exchange with Cd(2+) under exactly the same reaction conditions, purifying Cd1-xMnxSe nanocrystals back to CdSe nanocrystals with fine tunability. These chemistries offer exceptional composition control in Cd1-xMnxSe NCs, providing opportunities for fundamental studies of impurity diffusion in nanocrystals and for development of compositionally tuned nanocrystals with diverse applications ranging from solar energy conversion to spin-based photonics.

Absorption and Magnetic Circular Dichroism Analyses of Giant Zeeman Splittings in Diffusion-Doped Colloidal Cd(1-x)Mn(x)Se Quantum Dots.

Impurity ions can transform the electronic, magnetic, or optical properties of colloidal quantum dots. Magnetic impurities introduce strong dopant-carrier exchange coupling that generates giant Zeeman splittings (ΔEZ) of excitonic excited states. To date, ΔEZ in colloidal doped quantum dots has primarily been quantified by analysis of magnetic circular dichroism (MCD) intensities and absorption line widths (σ). Here, we report ΔEZ values detected directly by absorption spectroscopy for the first time in such materials, using colloidal Cd(1-x)Mn(x)Se quantum dots prepared by diffusion doping. A convenient method for decomposing MCD and absorption data into circularly polarized absorption spectra is presented. These data confirm the widely applied MCD analysis in the low-field, high-temperature regime, but also reveal a breakdown at low temperatures and high fields when ΔEZ/σ approaches unity, a situation not previously encountered in doped quantum dots. This breakdown is apparent for the first time here because of the extraordinarily large ΔEZ and small σ achieved by nanocrystal diffusion doping.

Picosecond Dynamics of Excitonic Magnetic Polarons in Colloidal Diffusion-Doped Cd(1-x)Mn(x)Se Quantum Dots.

Spontaneous magnetization is observed at zero magnetic field in photoexcited colloidal Cd(1-x)Mn(x)Se (x = 0.13) quantum dots (QDs) prepared by diffusion doping, reflecting strong Mn(2+)-exciton exchange coupling. The picosecond dynamics of this phenomenon, known as an excitonic magnetic polaron (EMP), are examined using a combination of time-resolved photoluminescence, magneto-photoluminescence, and Faraday rotation (TRFR) spectroscopies, in conjunction with continuous-wave absorption, magnetic circular dichroism (MCD), and magnetic circularly polarized photoluminescence (MCPL) spectroscopies. The data indicate that EMPs form with random magnetization orientations at zero external field, but their formation can be directed by an external magnetic field. After formation, however, external magnetic fields are unable to reorient the EMPs within the luminescence lifetime, implicating anisotropy in the EMP potential-energy surfaces. TRFR measurements in a transverse magnetic field reveal rapid (<5 ps) spin transfer from excitons to Mn(2+) followed by coherent EMP precession at the Mn(2+) Larmor frequency for over a nanosecond. A dynamical TRFR phase inversion is observed during EMP formation attributed to the large shifts in excitonic absorption energies during spontaneous magnetization. Partial optical orientation of the EMPs by resonant circularly polarized photoexcitation is also demonstrated. Collectively, these results highlight the extraordinary physical properties of colloidal diffusion-doped Cd(1-x)Mn(x)Se QDs that result from their unique combination of strong quantum confinement, large Mn(2+) concentrations, and relatively narrow size distributions. The insights gained from these measurements advance our understanding of spin dynamics and magnetic exchange in colloidal doped semiconductor nanostructures, with potential ramifications for future spin-based information technologies.

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.

Electronic Structure of a CuII–Alkoxide Complex Modeling Intermediates in Copper-Catalyzed Alcohol Oxidations

In the copper-catalyzed oxidation of alcohols to aldehydes, a Cu(II)-alkoxide (Cu(II)-OR) intermediate is believed to modulate the αC-H bond strength of the deprotonated substrate to facilitate the oxidation. As a structural model for these intermediates, we characterized the electronic structure of the stable compound Tp(tBu)Cu(II)(OCH2CF3) (Tp(tBu) = hydro-tris(3-tert-butyl-pyrazolyl)borate) and investigated the influence of the trifluoroethoxide ligand on the electronic structure of the complex. The compound exhibits an electron paramagnetic resonance (EPR) spectrum with an unusually large gzz value of 2.44 and a small copper hyperfine coupling Azz of 40 × 10(-4) cm(-1) (120 MHz). Single-crystal electron nuclear double resonance (ENDOR) spectra show that the unpaired spin population is highly localized on the copper ion (≈68%), with no more than 15% on the ethoxide oxygen. Electronic absorption and magnetic circular dichroism (MCD) spectra show weak ligand-field transitions between 5000 and 12,000 cm(-1) and an intense ethoxide-to-copper charge transfer (LMCT) transition at 24,000 cm(-1), resulting in the red color of this complex. Resonance Raman (rR) spectroscopy reveals a Cu-O stretch mode at 592 cm(-1). Quantum chemical calculations support the interpretation and assignment of the experimental data. Compared to known Cu(II)-thiolate and Cu(II)-alkylperoxo complexes from the literature, we found an increased σ interaction in the Cu(II)-OR bond that results in the spectroscopic features. These insights lay the basis for further elucidating the mechanism of copper-catalyzed alcohol oxidations.

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.

Excitonic Zeeman splittings in colloidal CdSe quantum dots doped with single magnetic impurities

Doping a semiconductor quantum dot with just a single impurity atom can completely transform its physical properties. Here, we report and analyze the magnetic circular dichroism (MCD) spectra of colloidal CdSe quantum dot samples containing on average fewer than one Mn2+ per quantum dot. Even at this sub-single-dopant level, the low-temperature low-field data are dominated by impurity-induced Zeeman splittings caused by dopant–carrier sp–d exchange. Unlike in more heavily doped quantum dots, however, the MCD intensity at the first CdSe exciton shows a field-induced sign flip as the field strength is increased, reflecting competition between sp–d exchange and the intrinsic Zeeman splittings of comparable magnitude. Most unusually, the competition between these two effects leads to a large apparent shift in the first MCD peak maximum, which we show is attributable to a difference in sign of the intrinsic excitonic g factor between the first and second excitons. Finally, the sp–d and intrinsic contributions to the excitonic Zeeman splittings each exhibit unique magnetic-field and temperature dependencies, allowing the MCD spectra of undoped, singly doped, and bi-doped quantum dot sub-ensembles to be analyzed.

Electrical Detection of Quantum Dot Hot Electrons Generated via a Mn2+-Enhanced Auger Process

An all-solid-state quantum-dot-based photon-to-current conversion device is demonstrated that selectively detects the generation of hot electrons. Photoexcitation of Mn2+-doped CdS quantum dots embedded in the device is followed by efficient picosecond energy transfer to Mn2+ with a long-lived (millisecond) excited-state lifetime. Electrons injected into the QDs under applied bias then capture this energy via Auger de-excitation, generating hot electrons that possess sufficient energy to escape over a ZnS blocking layer, thereby producing current. This electrically detected hot-electron generation is correlated with a quench in the steady-state Mn2+ luminescence and the introduction of a new nonradiative excited-state decay process, consistent with electron-dopant Auger cross-relaxation. The devices efficiency at detecting hot-electron generation provides a model platform for the study of hot-electron ionization relevant to the development of novel photodetectors and alternative energy-conversion devices.