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The photovoltaic and optoelectronic properties of lead halide perovskite semiconductors are controlled by excitons, so that investigation of their fundamental properties is of critical importance. The exciton Land\'e or g-factor g_X is the key parameter, determining the exciton Zeeman spin splitting in magnetic fields. The exciton, electron and hole carrier g-factors provide information on the band structure, including its anisotropy, and the parameters contributing to the electron and hole effective masses. We measure g_X by reflectivity in magnetic fields up to 60 T for lead halide perovskite crystals. The materials band gap energies at a liquid helium temperature vary widely across the visible spectral range from 1.520 up to 3.213 eV in hybrid organic-inorganic and fully inorganic perovskites with different cations and halogens: FA_{0.9}Cs_{0.1}PbI_{2.8}Br_{0.2], MAPbI_{3}, FAPbBr_{3}, CsPbBr_{3}, and MAPb(Br_{0.05}Cl_{0.95})_{3}. We find the exciton g-factors to be nearly constant, ranging from +2.3 to +2.7. Thus, the strong dependences of the electron and hole g-factors on the band gap roughly compensate each other when combining to the exciton g-factor. The same is true for the anisotropies of the carrier g-factors, resulting in a nearly isotropic exciton g-factor. The experimental data are compared favorably with model calculation results.

The recent observation of cyclotron resonance in optimally-doped La$_{2-x}$Sr$_x$CuO$_4$ using time-domain THz spectroscopy in high magnetic field has given new possibilities for the study of cuprate superconductors. One can measure the cyclotron mass in more disordered cuprates possesing short scattering times therefore expanding the study to materials and dopings in which quantum oscillations have not been observed. Here we present the measurement of the carrier mass of the hole doped cuprate La$_{2-x}$Sr$_x$CuO$_4$ across a a range of dopings spanning the slightly underdoped ($x=0.13$) to highly overdoped ($x=0.26$), near to the termination of the superconducting dome. These results reveal a systematic increase of $m_c$ with doping, up to values greater than thirteen times the bare electron mass. This is in contrast with those masses extracted from the heat capacity, which show a peak near the pseudogap critical point $p^*$ and/or Lifshitz transition. The cyclotron frequency is linear in field up to 31 T for all dopings giving no evidence for field induced Fermi surface reconstructions. The cyclotron mass is found to be positive for all dopings, but with a magnitude systematically below the heat capacity mass for under and optimally doped samples, while exceeding it for overdoped samples. Among other aspects, these results are surprising as photoemission reveals a Lifshitz transition in the middle of our doping range and the sign of the cyclotron mass determined from a finite frequency resonance is -- in conventional theories -- a {\it topological quantity} only sensitive to whether or not the Fermi surface is closed around holes or electrons. We see no sign of a divergence of the mass near $p^*$ nor near the Lifshitz transition, showing that any singularity -- if it exists -- is not strong enough to affect the cyclotron mass., Comment: 9 pages, 4 figures

Using time-domain terahertz spectroscopy in pulsed magnetic fields up to 31 T, we measure the terahertz optical conductivity in an optimally-doped thin film of the high temperature superconducting cuprate La$_{1.84}$Sr$_{0.16}$CuO$_4$. We observe systematic changes in the circularly-polarized complex optical conductivity that are consistent with cyclotron absorption of p-type charge carriers characterized by a cyclotron mass of $4.9\pm 0.8$ $m_{\rm e}$, and a scattering rate that increases with magnetic field. These results open the door to studies aimed at characterizing the degree to which electron-electron interactions influence carrier masses in cuprate superconductors., 6 pages, 4 figures

Understanding the nature and energy distribution of optical resonances is of central importance in low-dimensional materials$^{1-4}$ and its knowledge is critical for designing efficient optoelectronic devices. Ruddlesden-Popper halide perovskites are 2D solution-processed quantum wells with a general formula A$_2$A'$_{n-1}$M$_n$X$_{3n+1}$, where optoelectronic properties can be tuned by varying the perovskite layer thickness (n value), and have recently emerged as efficient semiconductors with technologically relevant stability. However, fundamental questions concerning the nature of optical resonances (excitons or free-carriers) and the exciton reduced mass, and their scaling with quantum well thickness remains unresolved. Here, using optical spectroscopy and 60-Tesla magneto-absorption supported by modelling, we unambiguously demonstrate that the optical resonances arise from tightly bound excitons with unexpectedly high exciton reduced mass (0.20 m0) and binding energies varying from 470 meV to 125 meV with increasing thickness from n=1 to 5. Our work demonstrates the dominant role of Coulomb interactions in 2D solution-processed quantum wells and presents unique opportunities for next-generation optoelectronic and photonic devices., 21 pages, 5 figures

International audience; Using time-resolved Kerr rotation, we measure the spin-valley dynamics of resident electrons and holes in single charge-tunable monolayers of the archetypal transition-metal dichalcogenide (TMD) semiconductor WSe2. In the n-type regime, we observe long (∼130 ns) polarization relaxation of electrons that is sensitive to in-plane magnetic fields By, indicating spin relaxation. In marked contrast, extraordinarily long (∼2 μs) polarization relaxation of holes is revealed in the p-type regime, which is unaffected by By, directly confirming long-standing expectations of strong spin-valley locking of holes in the valence band of monolayer TMDs. Supported by continuous-wave Kerr spectroscopy and Hanle measurements, these studies provide a unified picture of carrier polarization dynamics in monolayer TMDs, which can guide design principles for future valleytronic devices.

Using time-resolved Kerr rotation, we measure the spin/valley dynamics of resident electrons and holes in single charge-tunable monolayers of the archetypal transition-metal dichalcogenide (TMD) semiconductor WSe2. In the n-type regime, we observe long (70 ns) polarization relaxation of electrons that is sensitive to in-plane magnetic fields $B_y$, indicating spin relaxation. In marked contrast, extraordinarily long (2 microsecond) polarization relaxation of holes is revealed in the p-type regime, that is unaffected by $B_y$, directly confirming long-standing expectations of strong spin-valley locking of holes in the valence band of monolayer TMDs. Supported by continuous-wave Kerr spectroscopy and Hanle measurements, these studies provide a unified picture of carrier polarization dynamics in monolayer TMDs, which can guide design principles for future valleytronic devices., Comment: 5 pages, 3 figures

We use spectrally-resolved magneto-electroluminescence (EL) measurements to study the energy dependence of hyperfine interactions between polaron and nuclear spins in organic LEDs. Using layered devices based on Bphen/MTDATA -- a well-known exciplex emitter -- we show that the increase in EL emission intensity $I$ due to small applied magnetic fields of order 100 mT is markedly larger at the high-energy blue end of the EL spectrum (dI/I ~11%) than at the low-energy red end (~4%). Concurrently, the widths of the magneto-EL curves increase monotonically from blue to red, revealing an increasing hyperfine coupling between polarons and nuclei and directly providing insight into the energy-dependent spatial extent and localization of polarons., Comment: 4 pages, 4 figures

We report magneto-photoluminescence studies of strongly quantum-confined "0-D" diluted magnetic semiconductors (DMS), realized in Mn$^{2+}$-doped ZnSe/CdSe core/shell colloidal nanocrystals. In marked contrast to their 3-D (bulk), 2-D (quantum well), 1-D (quantum wire), and 0-D (self-assembled quantum dot) DMS counterparts, the ubiquitous yellow emission band from internal \emph{d-d} ($^4T_1 \rightarrow ^6A_1$) transitions of the Mn$^{2+}$ ions in these nanocrystals is \emph{not} suppressed in applied magnetic fields and \emph{does} become circularly polarized. This polarization tracks the Mn$^{2+}$ magnetization, and is accompanied by a sizable energy splitting between right- and left-circular emission components that scales with the exciton-Mn \emph{sp-d} coupling strength (which, in turn, is tunable with nanocrystal size). These data highlight the influence of strong quantum confinement on both the excitation and the emission mechanisms of magnetic ions in DMS nano-materials., Comment: To appear in Physical Review Letters

We report a comprehensive study of stochastic electron spin fluctuations -- spin noise -- in lightly doped ($n$-type) bulk GaAs, which are measured using sensitive optical magnetometry based on off-resonant Faraday rotation. Frequency spectra of electron spin noise are studied as a function of electron density, magnetic field, temperature, probe laser wavelength and intensity, and interaction volume. Electron spin lifetimes $\tau_s$ are inferred from the width of the spin noise spectra, and are compared with direct measurements of $\tau_s$ using conventional Hanle effect methods. Both methods reveal a strong and similar dependence of $\tau_s$ on the wavelength and intensity of the probe laser, highlighting the undesired influence of sub-bandgap absorption effects on the nominally `non-perturbative' spin noise measurements. As a function of temperature, the spin noise power increases approximately linearly from 1.5 K to 30 K, as expected for degenerate electrons obeying Fermi-Dirac statistics, but with an additional zero-temperature offset. Finally, as the cross-sectional area of the probe laser shrinks and fewer electrons are probed, the measured Faraday rotation fluctuations due to electron spin noise are shown to increase, as expected., Comment: 11 pages, 8 figs

We study the low-temperature magneto-photoluminescence (PL) from individual CdSe nanocrystals. Nanocrystals having a small "bright" exciton fine structure splitting ($$1 meV) show an anomalous magneto-PL polarization, wherein the lower-energy peak becomes circularly polarized with increasing field, while the higher-energy peak remains linearly polarized. This unusual behavior arises from strong mixing between the absorbing and emitting bright exciton levels due to strong anisotropic exchange interactions., Comment: 15 pages, 3 figures; submitted

We study the temperature-dependent modifications of trion and exciton photoluminescence (PL) spectra in modulation-doped CdTe/CdMgTe quantum wells in high magnetic field. We find that, in magnetic field, the temperature-dependent redistribution of exciton and trion PL intensities is opposite to that expected from a simple Boltzmann distribution model. Solving a system of rate equations that describe the exciton-trion energy levels, we calculate the temperature dependence of the exciton and trion PL intensities. The calculations show good agreement with the experimental data.

Coupled magneto-exciton states between allowed (`bright') and forbidden (`dark') transitions are found in absorption spectra of strained In$_{0.2}$Ga$_{0.8}$As/GaAs quantum wells with increasing magnetic field up to 30 T. We found large (~ 10 meV) energy splittings in the mixed states. The observed anticrossing behavior is independent of polarization, and sensitive only to the parity of the quantum confined states. Detailed experimental and theoretical investigations indicate that the excitonic Coulomb interaction rather than valence band complexity is responsible for the splittings. In addition, we determine the spin composition of the mixed states., Comment: 4 pages, 4 figures

We report polarized optical reflectance studies of \alpha'-NaV2O5 as a function of temperature (4-45 K) and magnetic field (0-60 T). Rung directed electronic structure changes, as measured by near-infrared reflectance ratios \Delta R(H)=R(H)/R(H=0 T), are especially sensitive to the phase boundaries. We employ these changes to map out an H-T phase diagram. Topological highlights include the observation of two phase boundaries slightly below T_{SG}, enhanced curvature of the 34 K phase boundary above 35 T, and, surprisingly, strong hysteresis effects of both transitions with applied field., Comment: 4 pages, 3 figures, PRB accepted

Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II-VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (VS) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. VS-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the VS are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.

The controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool which enables to engineer their physical properties. One compelling example is represented by metal chalcogenide NCs incorporating heterovalent p-type impurities such as d10 coinage metals (Cu+, Ag+, or Au+). In this type of nanostructures the interplay between the dopant and the host semiconductor energy levels leads in the ultra-fast capture of the hole by the localized state of the dopant leading to the so-called "acceptor-bound" excitons. The control of this paradigm unlocked technologically relevant functionalities, such as Stokes-shift between the emission and the absorptionspectra, extended luminescence lifetimes, photomagnetic behaviors, and enhanced electrical transport. To date, although conceptually analogous to hole-management schemes, the opposite "donor-bound" exciton scheme using aliovalent elements adopted to n-doped NCs (e.g., Al3+ and In3+ in) has not been realized due to the natural propensity of such cations to produce shallow donor states that inject electrons directly in the CB. Here, we exploit the propensity of metal sulfides to present sulfur vacancies (VS) that introduce a localized level pinned about 1 eV below the CB to produce a model system for "donor-bound" excitons in CdSeS NCs. The investigation of the optical and magneto-optical properties of these NCs revealed that the VS state is responsible for the ultrafast capture of electron in the CB which can then either decay non-radiatively or recombine with the VB photohole leading to long-lived, Stokes-shifted emission with size-tunable energy. Moreover, VS-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the VS are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photo-hole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor localized electron.

"Charge engineering" of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as "quantized" dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au + species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au + to paramagnetic Au 2+ (5d 9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach toward NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.

Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.

Ternary I-III-VI2 nanocrystals (NCs), such as CuInS2, are receiving attention as heavy-metals-free materials for solar cells, luminescent solar concentrators (LSCs), LEDs, and bio-imaging. The origin of the optical properties of CuInS2 NCs are however not fully understood. A recent theoretical model suggests that their characteristic Stokes-shifted and long-lived luminescence arises from the structure of the valence band (VB) and predicts distinctive optical behaviours in defect-free NCs: the quadratic dependence of the radiative decay rate and the Stokes shift on the NC radius. If confirmed, this would have crucial implications for LSCs as the solar spectral coverage ensured by low-bandgap NCs would be accompanied by increased re-absorption losses. Here, by studying stoichiometric CuInS2 NCs, it is revealed for the first time the spectroscopic signatures predicted for the free band-edge exciton, thus supporting the VB-structure model. At very low temperatures, the NCs also show dark-state emission likely originating from enhanced electron-hole spin interaction. The impact of the observed optical behaviours on LSCs is evaluated by Monte Carlo ray-tracing simulations. Based on the emerging device design guidelines, optical-grade large-area (30x30 cm(2)) LSCs with optical power efficiency (OPE) as high as 6.8% are fabricated, corresponding to the highest value reported to date for large-area devices.

Colloidal CdSe nanocrystals (NCs) overcoated with an ultrathick CdS shell, also known as dot-in-bulk (DiB) structures, can support two types of excitons, one of which is core-localized and the other, shell-localized. In the case of weak "sub-single-exciton" pumping, emission alternates between the core- and shell-related channels, which leads to two-color light. This property makes these structures uniquely suited for a variety of photonic applications as well as ideal model systems for realizing complex excitonic quasi-particles that do not occur in conventional core/shell NCs. Here, we show that the DiB design can enable an unusual regime in which the same long-lived resident electron can endow trionlike characteristics to either of the two excitons of the DiB NC (core- or shell-based). These two spectrally distinct trion states are apparent in the measured photoluminescence (PL) and spin dynamics of core and shell excitons conducted over a wide range of temperatures and applied magnetic fields. Low-temperature PL measurements indicate that core- and shell-based trions are characterized by a nearly ideal (∼100%) emission quantum yield, suggesting the strong suppression of Auger recombination for both types of excitations. Polarization-resolved PL experiments in magnetic fields of up to 60 T reveal that the core- and the shell-localized trions exhibit remarkably similar spin dynamics, which in both cases are controlled by spin-flip processes involving a heavy hole.

Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag+ is an emerging electronic dopant in III-V and II-VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag+ is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag+. This optical activation process and the associated modification of the electronic configuration of Ag+ remain unclear. Here, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag+ to paramagnetic Ag2+. The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.

In semiconductors, quantum confinement can greatly enhance the interaction between band carriers (electrons and holes) and dopant atoms. One manifestation of this enhancement is the increased stability of exciton magnetic polarons in magnetically-doped nanostructures. In the limit of very strong 0D confinement that is realized in colloidal semiconductor nanocrystals, a single exciton can exert an effective exchange field $B_{\rm{ex}}$ on the embedded magnetic dopants that exceeds several tesla. Here we use the very sensitive method of resonant photoluminescence (PL) to directly measure the presence and properties of exciton magnetic polarons in colloidal Cd$_{1-x}$Mn$_x$Se nanocrystals. Despite small Mn$^{2+}$ concentrations ($x$=0.4-1.6\%), large polaron binding energies up to $\sim$26~meV are observed at low temperatures via the substantial Stokes shift between the pump laser and the resonant PL maximum, indicating nearly complete alignment of all Mn$^{2+}$ spins by $B_{\rm{ex}}$. Temperature and magnetic field-dependent studies reveal that $B_{\rm{ex}} \approx$ 10~T in these nanocrystals, in good agreement with theoretical estimates. Further, the emission linewidths provide direct insight into the statistical fluctuations of the Mn$^{2+}$ spins. These resonant PL studies provide detailed insight into collective magnetic phenomena, especially in lightly-doped nanocrystals where conventional techniques such as nonresonant PL or time-resolved PL provide ambiguous results., Comment: 12 pages, 8 figures, Nano Letters articles ASAP (2017)

We have developed a new class of colloidal nanocrystals composed of Cu-doped ZnSe cores overcoated with CdSe shells. Via spectroscopic and magneto-optical studies, we conclusively demonstrate that Cu impurities represent paramagnetic +2 species and serve as a source of permanent optically active holes. This implies that the Fermi level is located below the Cu(2+)/Cu(1+) state, that is, in the lower half of the forbidden gap, which is a signature of a p-doped material. It further suggests that the activation of optical emission due to the Cu level requires injection of only an electron without a need for a valence-band hole. This peculiar electron-only emission mechanism is confirmed by experiments in which the titration of the nanocrystals with hole-withdrawing molecules leads to enhancement of Cu-related photoluminescence while simultaneously suppressing the intrinsic, band-edge exciton emission. In addition to containing permanent optically active holes, these newly developed materials show unprecedented emission tunability from near-infrared (1.2 eV) to the blue (3.1 eV) and reduced losses from reabsorption due to a large Stokes shift (up to 0.7 eV). These properties make them very attractive for applications in light-emission and lasing technologies and especially for the realization of novel device concepts such as "zero-threshold" optical gain.

Using semiconductor nanocrystals (NCs) one can produce extremely strong spatial confinement of electronic wave functions not accessible with other types of nanostructures. As a result, NCs exhibit important physical properties which, in combination with the chemical stability and solution processability, make this class of functional materials particularly appealing for several technological fields, such as solid-state lighting, lasers, photovoltaics, and electronics. Generally, the tunability of their physical properties is achieved through particle-size control of the quantum confinement effect. Wavefunction engineering adds a degree of freedom for manipulating the physical properties of NCs by selectively confining the carriers in specific domains of the material, thereby controlling the spatial overlap between the electron and hole wavefunctions. This design has been applied to several material systems in different geometries and has been shown to successfully control the emission energy and recombination dynamics as well as to reduce nonradiative Auger recombination, a process in which, as a consequence of strong spatial confinement, the energy of one electron-hole pair is nonradiatively transferred to a third charge carrier. The focus of this presentation is on nanocrystal heterostructures that comprise a small CdSe core overcoated with a thick shell of wider-gap CdS. These quasi-type II structures show greatly suppressed Auger recombination, which allows us to realize broadband optical gain (extends over 500 meV), and are a remarkable class of model compounds for investigating the influence of nanoengineered electron-hole overlap on the exciton fine structure. We indeed recently showed that this quasi-type II motif can be used to tune the energy splitting between optically active ("bright") and optically passive ("dark") excitons due to strong electron-hole exchange interaction, which is typical of quantum-confined semiconductor nanocrystals. This design provides a new tool for controlling excitonic dynamics including absolute recombination time scales and temperature and magnetic field dependences separately from the confinement energy. As a result of reduced Auger recombination, in combination with essentially complete suppression of energy-transfer in thick-shell NCs films, we recently fabricated bright, monochrome LEDs based on these nanostructures. Our results indicate that the luminance and efficiency can be improved dramatically by increasing the shell thickness without detrimental effects of increased turn-on voltage. Detailed structural and spectroscopic studies reveal a crucial role of interfaces on the Auger recombination process ion these heterostructures. Specifically, we observe a sharp transition to Auger-recombination-free behavior for shell thickness ∼1.8-2.5 nm, accompanied by the development of an intense phonon mode characteristic of a CdSeS alloy. These results suggest that the likely reason for suppressed Auger recombination in these nanostructures is the "smoothing out" of the otherwise sharp confinement potential due to formation of a graded interfacial CdSeS layer between the CdSe core and the CdS shell, as was recently proposed by theoretical calculations by Cragg and Efros. © 2012 SPIE.

Nanoscale materials have been investigated extensively for applications in memory and data storage. Recent advances include memories based on metal nanoparticles1, nanoscale phase-change materials2 and molecular switches3. Traditionally, magnetic storage materials make use of magnetic fields to address individual storage elements. However, new materials with magnetic properties addressable via alternative means (for example, electrical or optical) may lead to improved flexibility and storage density and are therefore very desirable. Here, we demonstrate that copper-doped chalcogenide nanocrystals exhibit not only the classic signatures of diluted magnetic semiconductors4—namely, a strong spin-exchange interaction between paramagnetic Cu2+ dopants and the conduction/valence bands of the host semiconductor—but also show a pronounced and long-lived photoinduced enhancement of their paramagnetic response. Magnetic circular dichroism studies reveal that paramagnetism in these nanocrystals can be controlled and increased by up to 100% when illuminated with above-gap (blue/ultraviolet) light. These materials retain a memory of the photomagnetization for hour-long timescales in the dark, with effects persisting up to ∼80 K. Magnetic circular dichroism reveals an enhancement of paramagnetism in copper-doped ZnSe–CdSe nanoscrystals and that the enhancement persists for hours in the dark.

A strong electron–hole exchange interaction (EI) in semiconductor nanocrystals (NCs) gives rise to a large (up to tens of meV) splitting between optically active ('bright') and optically passive ('dark') excitons. This dark–bright splitting has a significant effect on the optical properties of band-edge excitons and leads to a pronounced temperature and magnetic field dependence of radiative decay. Here we demonstrate a nanoengineering-based approach that provides control over EI while maintaining nearly constant emission energy. We show that the dark–bright splitting can be widely tuned by controlling the electron–hole spatial overlap in core–shell CdSe/CdS NCs with a variable shell width. In thick-shell samples, the EI energy reduces to, Electron–hole exchange interaction is an intrinsic property of semiconductors, which affects their fine structure. Brovelli et al. demonstrate a nanoengineering-based approach that provides control over the exchange interaction energy at nearly constant emission energy, which cannot be carried out using core-only nanocrystals.

Spatial confinement of electronic excitations in semiconductor nanocrystals (NCs) results in a significant enhancement of nonradiative Auger recombination (AR), such that AR processes can easily dominate the decay of multiexcitons. AR is especially detrimental to lasing applications of NCs, as optical gain in these structures explicitly relies on emission from multiexciton states. In standard NCs, AR rates scale linearly with inverse NC volume. Here, we investigate multiexciton dynamics in hetero-NCs composed of CdSe cores and CdS shells of tunable thickness. We observe a dramatic decrease in the AR rates at the initial stage of shell growth, which cannot be explained by traditional volume scaling alone. Rather, fluorescence-line-narrowing studies indicate that the suppression of AR correlates with the formation of an alloy layer at the core-shell interface suggesting that this effect derives primarily from the "smoothing" of the confinement potential associated with interfacial alloying. These data highlight the importance of NC interfacial structure in the AR process and provide general guidelines for the development of new nanostructures with suppressed AR for future lasing applications.