Emission State Structure and Linewidth Broadening Mechanisms in Type-II CdSe/CdTe Core–Crown Nanoplatelets: A Combined Theoretical–Single Nanocrystal Optical Study

Type-II heterostructures are key elementary components in optoelectronic, photovoltaic, and quantum devices. The staggered band alignment of materials leads to the stabilization of indirect excitons (IXs), i.e., correlated electron–hole pairs experiencing spatial separation with novel properties, boosting optical gain and promoting strategies for the design of information storage, charge separation, or qubit manipulation devices. Planar colloidal CdSe/CdTe core–crown type-II nested structures, grown as nanoplatelets (NPLs), are the focus of the present work. By combining low temperature single NPL measurements and electronic structure calculations, we gain insights into the mechanisms impacting the emission properties. We are able to probe the sensitivity of the elementary excitations (IXs, trions) with respect to the appropriate structural parameter (core size). Neutral IXs, with binding energies reaching 50 meV, are shown to dominate the highly structured single NPL emission. The large broadening linewidth that persists at the single NPL level clearly results from strong exciton–LO phonon coupling (Eph = 21 meV) whose strength is poorly influenced by trapped charges. The spectral jumps (≈10 meV) in the photoluminescence recorded as a function of time are explained by the fluctuations in the IX electrostatic environment considering fractional variations (≈0.2 e) of the noncompensated charge defects

Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors.

Engineering a low singlet-triplet energy gap (ΔEST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 105 cm-1) and a relatively large ΔEST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 μs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔEST in organic DF emitters

Spin-dependent Recombination in GaNAs

Spin filtering properties of novel GaNAs alloys are reported in this thesis. Spin-dependent recombination (SDR) in GaNAs via a deep paramagnetic defect center is intensively studied.  By using the optical orientation photoluminescence (PL) technique, GaNAs is shown to be able to spin filter electrons injected from GaAs, which is a useful functional property for integratition with future electronic devices.  The spin filtering ability is found to degrade in narrow GaNAs quantum well (QW) structures which is attributed to (i) acceleration of band-to-band recombination competing with the SDR process and to (ii) faster electron spin relaxation in the narrow QWs.  Ga interstitial-related defect centers have been found to be responsible for the SDR process by using the optically detected magnetic resonance (ODMR) technique. The defects are found to be the dominant grown-in defects in GaNAs, commonly formed during both MBE and MOCVD growths.  Methods to control the concentration of the Ga interstitials by varying doping, growth parameters and post-growth treatments are also examined

Room-temperature defect-engineered spin functionalities in Ga(In)NAs alloys

Semiconductor spintronics is one of the most interesting research fields that exploits both charge and spin properties for future photonics and electronic devices. Among many challenges of using spin in semiconductors, efficient generation of electron spin polarization at room temperature (RT) remains difficult. Recently, a new approach using defect-mediated spin filtering effect, employing -interstitial defects in Ga(In)NAs alloys, has been shown to turn the material into an efficient spin-polarized source capable of generating >40% conduction electron spin polarization at RT without an application of external fields. In order to fully explore the defectengineered spin functionalities, a better understanding and control of the spin filtering effects is required. This thesis work thus aims to advance our understanding, in terms of both physical and material insights, of the recently discovered spin filtering defects in Ga(In)NAs alloys. We have focused on the important issues of optimization and applications of the spin filtering effects. To improve spin filtering efficiency, important material and defect parameters must be addressed. Therefore, in Papers I–III formation of the  defects in Ga(In)NAs alloys has been examined under different growth and post-growth treatment conditions, as well as in different structures. We found that the  defects were the dominant and important nonradiative recombination centers in Ga(In)NAs epilayers and GaNAs/GaAs multiple quantum wells, independent of growth conditions and post-growth annealing. However, by varying growth and post-growth conditions, up to four configurations of the  defects, exhibiting different hyperfine  interaction (HFI) strengths between defect electron and nuclear (e-n) spins, have been found. This difference was attributed to different interstitial sites and/or complexes of  . Further studiesfocused on the effect of post-growth hydrogen (H) irradiation on the spin filtering effect. Beside the roles of H passivation of N resulting in bandgap reopening of the alloys, H treatment was shown to lead to complete quenching of the spin filtering effect, accompanied by strong suppression in the concentrations of the  defects. We concluded that the observed effect was due to the passivation of the  defects by H, most probably due to the formation of H- complexes. Optimizing spin filtering efficiency also requires detailed knowledge of spin interactions at the defect centers. This issue was addressed in Papers IV and V. From both experimental and theoretical studies, we were able to conclude that the HFI between e-n spins at the  defects led to e-n spin mixing, which degraded spin filtering efficiency at zero field.  Moreover, we have identified the microscopic origin of electron spin relaxation (T1) at the defect centers, that is, hyperfine-induced e-n spin cross-relaxation. Our finding thus provided a guideline to improve spin filtering efficiency by selectively incorporating the  defects with weak HFI by optimizing growth and post-growth treatment conditions, or by searching for new spin filtering defect centers containing zero nuclear spin. The implementation of the defect-engineered spin filtering effect has been addressed in Papers VI–VIII. First, we experimentally demonstrated for the first time at RT an efficient electron spin amplifier employing the  defects in Ga(In)NAs alloys, capable of amplifying a weak spin signal up to 27 times with a high cut-off frequency of 1 GHz. We further showed that the defectmediated spin amplification effect could turn the GaNAs alloy into an efficient RT optical spin detector. This enabled us to reliably conduct in-depth spin injection studies across a semiconductor heterointerface at RT. We found a strong reduction of electron spin polarization after optical spin injection from a GaAs layer into an adjacent GaNAs layer. This observation was attributed to severe spin loss across the heterointerface due to structural inversion asymmetry and probably also interfacial point defects. Finally, we went beyond the generation of strongly polarized electron spins. In Paper IX we focused on an interesting aspect of using strongly polarized electron spins to induce strong nuclear spin polarization at RT, relevant to solid-state quantum computation using a defect nuclear spin of long spin memory as a quantum bit (qubit). By combining the spin filtering effect and the HFI, we obtained a sizeable nuclear spin polarization of ~15% at RT that could be sensed by conduction electrons. This demonstrated the feasibility of controlling defect nuclear spins via conduction electrons even at RT, the first case ever being demonstrated in a semiconductor

Limiting factor of defect-engineered spin-filtering effect at room temperature

We identify hyperfine-induced electron and nuclear spin cross-relaxation as the dominant physical mechanism for the longitudinal electron spin relaxation time (T-1) of the spin-filtering Ga-i(2+) defects in GaNAs alloys. This conclusion is based on our experimental findings that T-1 is insensitive to temperature over 4-300 K, and its exact value is directly correlated with the hyperfine coupling strength of the defects that varies between different configurations of the Ga-i(2+) defects present in the alloys. These results thus provide a guideline for further improvements of the spin-filtering efficiency by optimizing growth and processing conditions to preferably incorporate the Ga-i(2+) defects with a weak hyperfine interaction and by searching for new spin-filtering defects with zero nuclear spin

Effect of hyperfine-induced spin mixing on the defect-enabled spin blockade and spin filtering in GaNAs

The effect of hyperfine interaction (HFI) on the recently discovered room-temperature defect-enabled spin-filtering effect in GaNAs alloys is investigated both experimentally and theoretically based on a spin Hamiltonian analysis. We provide direct experimental evidence that the HFI between the electron and nuclear spin of the central Ga atom of the spin-filtering defect, namely, the Ga-i interstitials, causes strong mixing of the electron spin states of the defect, thereby degrading the efficiency of the spin-filtering effect. We also show that the HFI-induced spin mixing can be suppressed by an application of a longitudinal magnetic field such that the electronic Zeeman interaction overcomes the HFI, leading to well-defined electron spin states beneficial to the spin-filtering effect. The results provide a guideline for further optimization of the defect-engineered spin-filtering effect. DOI: 10.1103/PhysRevB.87.125202Funding Agencies|Linkoping University through the professor contract, Swedish Research Council|621-2011-4254|Linkoping University through the professor contract Swedish Energy Agency||Knut and Alice Wallenberg Foundation||</p

Identifying a Generic and Detrimental Role of Fano Resonance in Spin Generation in Semiconductor Nanostructures

Fano resonance is a fundamental physical process that strongly affects the electronic transport, optical, and vibronic properties of matter. Here, we provide the first experimental demonstration of its profound effect on spin properties in semiconductor nanostructures. We show that electron spin generation in InAs/GaAs quantum-dot structures is completely quenched upon spin injection from adjacent InGaAs wetting layers at the Fano resonance due to coupling of light-hole excitons and the heavy-hole continuum of the interband optical transitions, mediated by an anisotropic exchange interaction. Using a master equation approach, we show that such quenching of spin generation is robust and independent of Fano parameters. This work therefore identifies spin-dependent Fano resonance as a universal spin loss channel in quantum-dot systems with an inherent symmetry-breaking effect.Funding Agencies|Swedish Research CouncilSwedish Research CouncilEuropean Commission [2016-05091, 2020-04530]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]</p

Effect of hyperfine-induced spin mixing on the defect-enabled spin blockade and spin filtering in GaNAs

The effect of hyperfine interaction (HFI) on the recently discovered room-temperature defect-enabled spin-filtering effect in GaNAs alloys is investigated both experimentally and theoretically based on a spin Hamiltonian analysis. We provide direct experimental evidence that the HFI between the electron and nuclear spin of the central Ga atom of the spin-filtering defect, namely, the Ga-i interstitials, causes strong mixing of the electron spin states of the defect, thereby degrading the efficiency of the spin-filtering effect. We also show that the HFI-induced spin mixing can be suppressed by an application of a longitudinal magnetic field such that the electronic Zeeman interaction overcomes the HFI, leading to well-defined electron spin states beneficial to the spin-filtering effect. The results provide a guideline for further optimization of the defect-engineered spin-filtering effect. DOI: 10.1103/PhysRevB.87.125202Funding Agencies|Linkoping University through the professor contract, Swedish Research Council|621-2011-4254|Linkoping University through the professor contract Swedish Energy Agency||Knut and Alice Wallenberg Foundation||</p

Temperature dependence of dynamic nuclear polarization and its effect on electron spin relaxation and dephasing in InAs/GaAs quantum dots

Electron spin dephasing and relaxation due to hyperfine interaction with nuclear spins is studied in an InAs/GaAs quantum dot ensemble as a function of temperature up to 85 K, in an applied longitudinal magnetic field. The extent of hyperfineinduced dephasing is found to decrease, whereas dynamic nuclear polarization increases with increasing temperature. We attribute both effects to an accelerating electron spin relaxation through phonon-assisted electron-nuclear spin flip-flops driven by hyperfine interactions, which could become the dominating contribution to electron spin depolarization at high temperatures.funding agencies|Swedish Research Council| 621-2011-4254