Spin-triplet Configuration Research Articles

Excited State Magneto-Structural Correlations Related to Photoinduced Electron Spin Polarization

Photoinduced electron spin polarization (ESP) is reported in the ground state of a series of complexes consisting of an organic radical (nitronylnitroxide, NN) covalently attached to a donor-acceptor chromophore either directly or via para-phenylene bridges substituted with 0-4 methyl groups. These molecules represent a class of chromophores that undergo visible light excitation to produce an initial exchange-coupled, three-spin [bpy•-, CAT•+ (= semiquinone, SQ) and NN•], charge-separated doublet 2S1 (S = chromophore spin singlet configuration) excited state that rapidly decays by magnetic exchange-enhanced internal conversion to a 2T1 (T = chromophore excited spin triplet configuration) state. The 2T1 state equilibrates with chromophoric and NN radical-derived excited states, resulting in absorptive ESP of the recovered ground state, which persists for greater than a millisecond and can be measured by low-temperature time-resolved electron paramagnetic resonance spectroscopy. The magnitude of the ground state ESP is found to correlate with the excited state magnetic exchange interaction between the CAT+• and NN• radicals, which in turn is controlled by the structure of the bridge fragment.

Excited State Exchange Control of Photoinduced Electron Spin Polarization in Electronic Ground States.

Ground-state electron spin polarization (ESP) is generated in radical elaborated (bpy)Pt(CAT-NN) and (bpy)Pt(CAT-p-Me2PhMe2-NN) (bpy = 5,5'-di-tert-butyl-2,2'-bipyridine, CAT = 3-tert-butylcatecholate, p-Ph = para-phenylene, NN = nitronylnitroxide). Photoexcitation produces an exchange-coupled, three-spin, charge-separated doublet 2S1 (S = chromophore excited spin singlet configuration) excited state that rapidly decays to a 2T1 (T = chromophore excited spin triplet configuration) excited state. The SQ-bridge-NN bond torsions affect the magnitude of the excited state exchange interaction (JSQ-NN), which determines the 2T1-4T1 energy gap. Ground state ESP is dependent on the magnitude of JSQ-NN, and we postulate that this results from differences in 2T1 and 4T1 state mixing. Mechanisms that lead to the rapid transfer of the excited state ESP to the ground state are discussed. Although subnanosecond 2T1 state lifetimes are measured optically in solution, the ground state ESP decays very slowly at 20 K and is observable for more than a millisecond.

Theory of Andreev blockade in a double quantum dot with a superconducting lead

A normal metal source reservoir can load two electrons onto a double quantum dot in the spin-triplet configuration. We show that if the drain lead of the dot is a spin-singlet superconductor, these electrons cannot form a Cooper pair and are blockaded on the double dot. We call this phenomenon Andreev blockade because it arises due to suppressed Andreev reflections. We identify transport characteristics unique to Andreev blockade. Most significantly, it occurs for any occupation of the dot adjacent to the superconductor, in contrast with the well-studied Pauli blockade which requires odd occupations. Andreev blockade is lifted if quasiparticles are allowed to enter the superconducting lead, but it should be observable in the hard gap superconductor-semiconductor devices. A recent experiment tests this model and finds support for several predictions made here [P. Zhang, H. Wu, J. Chen, S. A. Khan, P. Krogstrup, D. Pekker, and S. M. Frolov, arXiv:2102.03283 (2021)]. Andreev blockade should be considered in the design of topological quantum circuits, hybrid quantum bits and quantum emulators.

Metal Ion Control of Photoinduced Electron Spin Polarization in Electronic Ground States.

Both the sign and intensity of photoinduced electron spin polarization (ESP) in the electronic ground state doublet (2S0/D0) of chromophore-radical complexes can be controlled by changing the nature of the metal ion. The complexes consist of an organic radical (nitronyl nitroxide, NN) covalently attached to a donor-acceptor chromophore via a m-phenylene bridge, (bpy)M(CAT-m-Ph-NN) (1) (bpy = 4,4'-di-tert-butyl-2,2'-bipyridine, M = PdII (1-Pd) or PtII (1-Pt), CAT = 3-tert-butylcatecholate, m-Ph = meta-phenylene). In both complexes, photoexcitation with visible light produces an initial exchange-coupled, three-spin (bpy•-, CAT•+ = semiquinone (SQ), and NN•), charge-separated doublet 2S1 (S = chromophore excited spin singlet configuration) excited state that rapidly decays to the ground state via a 2T1 (T = chromophore excited spin triplet configuration) state. This process is not expected to be spin selective, and only very weak emissive ESP is found for 1-Pd. In contrast, strong absorptive ESP is generated in 1-Pt. It is postulated that zero-field-splitting-induced transitions between the chromophoric 2T1 and 4T1 states (1-Pd and 1-Pt) and spin-orbit-induced transitions between 2T1 and NN-based quartet states (1-Pt) account for the differences in polarization.

Space charge control of point defect spin states in AlN

One barrier to developing quantum information systems based on impurity point defects is that the desirable spin states of the defects are often unstable for Fermi levels obtained at increased impurity concentrations. The space charge induced band bending near the interface of Si/Mg aluminum nitride (AlN) homojunction is investigated computationally as a method to control the concentration, spin state, and position of such point defects. This is done by solving Poisson's equation with the charge density described by a grand canonical defect chemistry model informed by hybrid-functional density functional theory (DFT) calculations. Previous experimental works have found unintentional carbon and oxygen impurities pervade AlN homojunctions. First principles calculations have predicted the neutral complex between an aluminum vacancy and oxygen impurity on a neighboring nitrogen site (vAl-1ON)0 has a spin triplet configuration, which is stable in a region when the Fermi level is below midgap. From defect equilibrium simulations considering 602 possible defects, vAl-1ON was found to be unstable on the Mg-doped side of the homojunction and isolated oxygen impurities are preferred. On the Si-doped side, vAl-1ON forms but as (vAl-1ON)–2, not (vAl-1ON)0. This makes vAl-1ON a prototypical test case for the proposed strategy. Simulations of the Si/Mg:AlN homojunction showed (vAl-1ON)0 is stabilized within 6 nm of the interface in the Si-doped portion. This result indicates space charge induced band bending enables control over the concentration, spin state, and position of point defects, which is critical to realizing point defect based quantum information systems.

Gate Tunable Dark Trions in Monolayer WSe_{2}.

Monolayer WSe_{2} is an intriguing material to explore dark exciton physics. We have measured the photoluminescence from dark excitons and trions in ultraclean monolayer WSe_{2} devices encapsulated by boron nitride. The dark trions can be tuned continuously between negative and positive trions with electrostatic gating. We reveal their spin-triplet configuration and distinct valley optical emission by their characteristic Zeeman splitting under a magnetic field. The dark trion binding energies are 14-16meV, slightly lower than the bright trion binding energies (21-35meV). The dark trion lifetime (∼1.3 ns) is two orders of magnitude longer than the bright trion lifetime (∼10 ps) and can be tuned between 0.4 and 1.3ns by gating. Such robust, optically detectable, and gate tunable dark trions may help us realize trion transport in two-dimensional materials.

Emerging photoluminescence from the dark-exciton phonon replica in monolayer WSe2

Tungsten-based monolayer transition metal dichalcogenides host a long-lived “dark” exciton, an electron-hole pair in a spin-triplet configuration. The long lifetime and unique spin properties of the dark exciton provide exciting opportunities to explore light-matter interactions beyond electric dipole transitions. Here we demonstrate that the coupling of the dark exciton and an optically silent chiral phonon enables the intrinsic photoluminescence of the dark-exciton replica in monolayer WSe2. Gate and magnetic-field dependent PL measurements unveil a circularly-polarized replica peak located below the dark exciton by 21.6 meV, equal to E″ phonon energy from Se vibrations. First-principles calculations show that the exciton-phonon interaction selectively couples the spin-forbidden dark exciton to the intravalley spin-allowed bright exciton, permitting the simultaneous emission of a chiral phonon and a circularly-polarized photon. Our discovery and understanding of the phonon replica reveals a chirality dictated emission channel of the phonons and photons, unveiling a new route of manipulating valley-spin.

Radiative cascade from quantum dot metastable spin-blockaded biexciton

We detect a novel radiative cascade from a neutral semiconductor quantum dot. The cascade initiates from a metastable biexciton state in which the holes form a spin-triplet configuration, Pauli-blockaded from relaxation to the spin-singlet ground state. The triplet biexciton has two photon-phonon-photon decay paths. Unlike in the singlet-ground state biexciton radiative cascade, in which the two photons are co-linearly polarized, in the triplet biexciton cascade they are crosslinearly polarized. We measured the two-photon polarization density matrix and show that the phonon emitted when the intermediate exciton relaxes from excited to ground state, preserves the exciton's spin. The phonon, thus, does not carry with it any which-path information other than its energy. Nevertheless, entanglement distillation by spectral filtering was found to be rather ineffective for this cascade. This deficiency results from the opposite sign of the anisotropic electron-hole exchange interaction in the excited exciton relative to that in the ground exciton.

Suppression of Kondo-assisted cotunneling in a spin-1 quantum dot with spin-orbit interaction

Kondo-type zero-bias anomalies have been frequently observed in quantum dots occupied by two electrons and attributed to a spin-triplet configuration that may become stable under particular circumstances. Conversely, zero-bias anomalies have been so far quite elusive when quantum dots are occupied by an even number of electrons greater than two, even though a spin-triplet configuration is more likely to be stabilized there than for two electrons. We propose as an origin of this phenomenon the spin-orbit interaction, and we show how it profoundly alters the conventional Kondo screening scenario in the simple case of a laterally confined quantum dot with four electrons.

Resonances of trion states in quantum dot molecules tuned by an electric field

The quantum states of the trion (two electrons and one hole ${X}^{\ensuremath{-}}$ or two holes and one electron ${X}^{+}$) in double quantum dots are theoretically investigated within the effective-mass approximation for a quasi-one-dimensional model: the numerical method employed is exact in the sense that it does not rely on basis-set expansions nor on perturbative or variational approaches. We have investigated the tuning by the electric field of the energy levels into resonance showing crossing and anticrossing patterns. The ground and the excited states, for the spin-singlet and spin-triplet configurations, are calculated and discussed. The electric-field dependent spectra for the ${X}^{\ensuremath{-}}$ and ${X}^{+}$ trions are similar, although they depend differently on the system parameters which define the confining potential. The oscillator strengths of the trion optical transitions are calculated for the first time for the double dot systems. For both types of trions, we found good agreement between calculations and the existing photoluminescence data obtained from vertically stacked double quantum dots. For a system of symmetric dots, we predict a parabolic dependence of the energy level of the triplet ground state on the electric field and substantially different patterns of the level anticrossings in the optical spectra.

Energy spectrum of centres in spherical quantum dots

The properties of negatively charged donor centres have been studied for semiconductor quantum dots with the finite spherically symmetric confinement potential. The energy levels of the ground state and the excited states of both the spin-singlet and spin-triplet configurations have been calculated by variational means. It has been shown that the excited states of the centre in quantum dots are bound for sufficiently strong confinement potential. The conditions of binding for the excited states have been determined as functions of the potential-well depth and quantum-dot radius. The formation of the bound excited states of the centre is a new property, which results from the confinement of electrons in the quantum dot. A possible application of the present results to the ion trapped in a microcavity is discussed.

Optical detection of magnetic resonance of FAand F centres in CaO:Mg

Optically detected magnetic resonance experiments on F and FA(Mg) centres in irradiated CaO:Mg crystals show that the sign and magnitude of the resonance signals are consistent with T1>or approximately= tau A for both defects. This means that resonance always occurs as an increase in the intensity of circularly polarised light. The wavelength dependence of these resonances is shown to have important consequences for the selective feeding of the excited-state spin triplet configurations. The data are consistent both with the polarised luminescence studies and the photoconversion of F centres and conversion of FA+ centres to FA centres reported by Welch and Hughes (1980).