Search

Organic free radicals related to the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical are known as photoluminescence-quenchers when coupled to group II-chalcogenide colloidal quantum dots (QDs), but the mechanism responsible for this phenomenon has so far remained unresolved. Using a combination of time-resolved photoluminescence and transient absorption spectroscopies, we demonstrate that photoexcited colloidal CdSe QDs coupled to 4-amino-TEMPO undergo highly efficient reductive quenching, that is, hole transfer from the valence band of the quantum dot to the organic paramagnetic species. Interestingly, the process is shown to occur on a subpicosecond time scale for bound 4AT; such a large rate constant for the extraction of holes from photoexcited CdSe QD by a molecular species is rare and underlines the potential that TEMPO derivatives can play in mediating efficient redox processes involving colloidal CdSe QDs.

There are few molecular precursors that chemically convert to nitride nanomaterials, which severely limits the development of this important class of materials. Alkylamides are soluble and stable nitride precursors that can be based on the same primary amines that are often used in colloidal nanomaterial synthesis, but their conversion involves the breaking of stable C-N bonds through a mechanism that remained unknown up to now. A critical aspect of this conversion mechanism is uncovered here, involving a prelimary step whereby alkylamides are oxidized to N-alkylimines to yield NH 2 - amide species that are postulated to be the actual reactive precursors in the formation of indium nitride nanomaterials. Interestingly, this step also involves the concomitant reduction of indium(III) to In(0) nanodroplets, which consequently catalyze the growth of InN nanomaterials. The elucidation of the origin of the surprising reactivity of otherwise stable molecular precursors opens the door to the development of new solution-phase approaches for the synthesis of nitride materials.

II-VI colloidal semiconductor nanocrystals (NCs), such as CdSe NCs, are often plagued by efficient nonradiative recombination processes that severely limit their use in energy-conversion schemes. While these processes are now well-known to occur at the surface, a full understanding of the exact nature of surface defects and of their role in deactivating the excited states of NCs has yet to be established, which is partly due to challenges associated with the direct probing of the complex and dynamic surface of colloidal NCs. Here, we report a detailed study of the surface of cadmium-rich zinc-blende CdSe NCs. The surfaces of these cadmium-rich species are characterized by the presence of cadmium carboxylate complexes (CdX 2 ) that act as Lewis acid (Z-type) ligands that passivate undercoordinated selenide surface species. The systematic displacement of CdX 2 from the surface by N,N,N',N'-tetramethylethylene-1,2-diamine (TMEDA) has been studied using a combination of 1 H NMR and photoluminescence spectroscopies. We demonstrate the existence of two independent surface sites that differ strikingly in the binding affinity for CdX 2 and that are under dynamic equilibrium with each other. A model involving coupled dual equilibria allows a full characterization of the thermodynamics of surface binding (free energy, as well as enthalpic and entropic terms), showing that entropic contributions are responsible for the difference between the two surface sites. Importantly, we demonstrate that cadmium vacancies only lead to important photoluminescence quenching when created on one of the two sites, allowing a complete picture of the surface composition to be drawn where each site is assigned to specific NC facet locale, with CdX 2 binding affinity and nonradiative recombination efficiencies that differ by up to two orders of magnitude.

Auger processes in colloidal semiconductor nanocrystals have been scrutinized extensively in recent years. Whether involving electron-exciton, hole-exciton, or exciton-exciton interactions, such Auger processes are generally fast and hence have been considered prominent candidates for interpreting fast processes relevant to photoluminescence blinking and multiexciton decay. With recent advances in the chemistries of nanocrystal doping, increasing attention is now being paid to analogous photophysical properties of colloidal-doped semiconductor nanocrystals. Here, we report the first investigation of the effects of electron-dopant exchange interactions on dopant luminescence in doped semiconductor nanocrystals. Using electrochemical techniques, electrical control of charge-carrier densities in films of colloidal Mn(2+)-doped CdS quantum dots has been achieved and used to demonstrate remarkably effective Auger de-excitation of photoexcited Mn(2+). The doped nanocrystals are found to be substantially more sensitive to Auger de-excitation than their undoped analogues, a result shown to arise primarily from the long Mn(2+) excited-state lifetime. This observation of exceptionally effective Auger quenching has broader implications in areas of high-power, single-particle, or electrically driven luminescence of doped semiconductor nanocrystals, and also suggests interesting opportunities for modulating Mn(2+) photoluminescence intensities on sublifetime time scales, or for imaging charge carriers in nanocrystal-based devices.

Colloidal manganese-doped semiconductor nanocrystals have been developed that show pronounced intrinsic high-temperature dual emission. Photoexcitation of these nanocrystals gives rise to strongly temperature dependent luminescence involving two distinct but interconnected emissive excited states of the same doped nanocrystals. The ratio of the two intensities is independent of nonradiative effects. The temperature window over which pronounced dual emission is observed can be tuned by changing the nanocrystal energy gap during growth. This unique combination of properties makes this new class of intrinsic dual emitters attractive for ratiometric optical thermometry applications.

Dopant-carrier magnetic exchange interactions in semiconductor nanostructures give rise to unusually large Zeeman splittings of the semiconductor band levels, raising possibilities for spin-based electronics or photonics applications. Here we evaluate the recently highlighted possibility of confinement-induced kinetic s-d exchange coupling in doped ZnSe/CdSe inverted core/shell nanocrystals. Magneto-optical studies of a broad series of Co(2+)- and Mn(2+)-doped core, inverted core/shell, and isocrystalline core/shell nanocrystals reveal that the dominant spectroscopic effects caused by CdSe shell growth around doped ZnSe core nanocrystals arise from hole spatial relaxation, being essentially independent of the electron-dopant interaction or the heterointerface itself. The general criteria for observation of kinetic s-d exchange coupling in doped nanocrystals are discussed in light of these results.

An attractive approach to controlling spin effects in semiconductor nanostructures for applications in electronics is the use of light to generate, manipulate, or read out spins. Here, we demonstrate spontaneous photoinduced polarization of manganese(II) spins in doped colloidal cadmium selenide quantum dots. Photoexcitation generates large dopant-carrier exchange fields, enhanced by strong spatial confinement, that lead to giant Zeeman splittings of the semiconductor band structure in the absence of applied magnetic fields. These internal exchange fields allow spontaneous magnetic saturation of the manganese(II) spins to be achieved at zero external magnetic field up to approximately 50 kelvin. Photomagnetic effects are observed all the way up to room temperature.

Colloidal Mn (2+)-doped CdSe quantum dots showing long excitonic photoluminescence decay times of up to tau exc = 15 mus at temperatures over 100 K are described. These decay times exceed those of undoped CdSe quantum dots by approximately 10 (3) and are shown to arise from the creation of excitons by back energy transfer from excited Mn (2+) dopant ions. A kinetic model describing thermal equilibrium between Mn (2+ 4)T 1 and CdSe excitonic excited states reproduces the experimental observations and reveals that, for some quantum dots, excitons can emit with near unity probability despite being approximately 100 meV above the Mn (2+ 4)T 1 state. The effect of Mn (2+) doping on CdSe quantum dot luminescence at high temperatures is thus completely opposite from that at low temperatures described previously.

Detailed low-temperature single-crystal polarized absorption and luminescence spectra of Cs2[CrCl2(H2O)4]Cl3 are reported. The luminescence spectrum is a broad band with a maximum at 11,800 cm (-1), indicating that the trans-[CrCl2(H2O)4]+ complex emits from a quartet excited state. The resolved vibronic structure reveals a progression in a nontotally symmetric 445 cm (-1) b1g mode, a manifestation of a Jahn-Teller effect in the emitting state. The absorption spectrum shows completely linearly polarized, magnetic-dipole-allowed electronic origins, defining the tetragonal splitting of the states originating from 4T2g (Oh). An energy gap of approximately 800 cm (-1) is observed between the electronic origins of the emitting state and the onset of the pi-polarized absorption spectrum. Both Jahn-Teller and spin-orbit couplings in the orbitally degenerate 4Eg (D4h) state are necessary to account for the spectroscopic observations.

The photoluminescence of colloidal Mn2+-doped CdSe nanocrystals has been studied as a function of nanocrystal diameter. These nanocrystals are shown to be unique among colloidal doped semiconductor nanocrystals reported to date in that quantum confinement allows tuning of the CdSe bandgap energy across the Mn2+ excited-state energies. At small diameters, the nanocrystal photoluminescence is dominated by Mn 2+ emission. At large diameters, CdSe excitonic photoluminescence dominates. The latter scenario has allowed spin-polarized excitonic photoluminescence to be observed in colloidal doped semiconductor nanocrystals for the first time.

The syntheses and X-ray structures of the complexes Ru(S-dmso)Cl2(opda) (1) and Ru(NH3)2Cl2(bqdi) (2) are described (opda= o-phenylenediamine, bqdi= o-benzoquinonediimine). Optical absorption and emission, vibrational (resonance Raman), and electrochemical data are discussed. We explore the nature of the ruthenium benzoquinone electronic interaction in species 2 primarily within the framework of density functional theory (DFT) but also using INDO/S to extract Coulombic and exchange integrals. The resonance Raman and emission data were understood in terms of a common set of coupled vibrations localized primarily within the ruthenium metallacycle ring. Experimental and computational data were also compared among a select group of ruthenium bqdi species with other spectator ligands, specifically ammonia, 2,2'-bipyridine, and 2,4-pentanedione. The changes in the electrochemistry, optical spectroscopy, and vibrational spectra with changing spectator ligand donicity were explained within a common theoretical (DFT) model which further provided a detailed analysis of the variation in the molecular orbital descriptions. With the application of an extended charge decomposition analysis (ECDA), a detailed picture emerged of the bonding between the bqdi ligand and the metal atom, illustrating the coupling between the orbitals of each fragment as a function of orbital symmetry and charge transfer between the fragments of the complex. Metal-to-bqdi pi-back-donation is seen to be very important.

The electronic structure of a trigonally distorted vanadium(III) complex, [V(urea)6](ClO4)3, and its deuterated analogue, [V(urea-d4)6](ClO4)3 has been investigated with Raman, luminescence, and high-frequency high-field electron paramagnetic resonance spectroscopies and with magnetic measurements. A broad electronic Raman transition is observed at around 1400 cm(-1) and attributed to a transition to the (3)E (D3) component of the (3)T1g (O(h)) ground state. The same splitting is seen in the near-infrared luminescence spectrum in the form of a similarly broad peak at 8450 cm(-1), 1400 cm(-1) lower in energy than the (1)E --> (3)A2 spin-flip transition. Powder high-frequency and high-field electron paramagnetic resonance spectra, magnetic susceptibilities, and magnetization studies give a precise measurement of the zero-field splitting and of the g values in this complex (D = 6.00(2) cm(-1), E = 0.573(6) cm(-1), g(x) = 1.848(2), g(y) = 1.832(4), and g(z) = 1.946(7)). A set of angular overlap model parameters is proposed that reproduces all spectroscopic observations, and an analysis of the influence of the bonding of urea on the trigonal distortion of the complex is given.