Spin-dependent Recombination Processes Research Articles

Optical Dependence of Electrically Detected Magnetic Resonance in Lightly Doped Si:P Devices

Electrically-detected magnetic resonance (EDMR) provides a highly sensitive method for reading out the state of donor spins in silicon. The technique relies on a spin-dependent recombination (SDR) process involving dopant spins that are coupled to interfacial defect spins near the Si/SiO$_2$ interface. To prevent ionization of the donors, the experiments are performed at cryogenic temperatures and the mobile charge carriers needed are generated via optical excitation. The influence of this optical excitation on the SDR process and the resulting EDMR signal is still not well understood. Here, we use EDMR to characterize changes to both phosphorus and defect spin readout as a function of optical excitation using: a 980 nm laser with energy just above the silicon band edge at cryogenic temperatures; a 405 nm laser to generate hot surface-carriers; and a broadband white light source. EDMR signals are observed from the phosphorus donor and two distinct defect species in all the experiments. With near-infrared excitation, we find that the EDMR signal primarily arises from donor-defect pairs, while at higher photon energies there are significant additional contributions from defect-defect pairs. The optical penetration depth into silicon is also known to be strongly wavelength dependent at cryogenic temperatures. The energy of the optical excitation is observed to strongly modulate the kinetics of the SDR process. Careful tuning of the optical photon energy could therefore be used to control both the subset of spin pairs contributing to the EDMR signal as well as the dynamics of the SDR process.

Morphology effects on spin-dependent transport and recombination in polyfluorene thin films

We have studied the role of spin-dependent processes on conductivity in polyfluorene (PFO) thin films by preforming continuous wave (cw) electrically detected magnetic resonance (EDMR) spectroscopy at temperatures between 10 K and room temperature using microwave frequencies between about 1 GHz and 20 GHz, as well as pulsed EDMR at the $X$ band (10 GHz). Variable frequency EDMR allows us to establish the role of spin-orbit coupling in spin-dependent processes whereas pulsed EDMR allows for the observation of coherent spin motion effects. We used PFO for this study in order to allow for the investigation of the effects of microscopic morphological ordering since this material can adopt two distinct intrachain morphologies: an amorphous (glassy) phase, in which monomer units are twisted with respect to each other, and an ordered (\ensuremath{\beta}) phase, where all monomers lie within one plane. In thin films of organic light-emitting diodes, the appearance of a particular phase can be controlled by deposition parameters and solvent vapor annealing, and is verified by electroluminescence spectroscopy. Under bipolar charge-carrier injection conditions, we conducted multifrequency cw EDMR, electrically detected Rabi spin-beat experiments, and Hahn echo and inversion-recovery measurements. Coherent echo spectroscopy reveals electrically detected electron-spin-echo envelope modulation due to the coupling of the carrier spins to nearby nuclear spins. Our results demonstrate that, while conformational disorder can influence the observed EDMR signals, including the sign of the current changes on resonance as well as the magnitudes of local hyperfine fields and charge-carrier spin-orbit interactions, it does not qualitatively affect the nature of spin-dependent transitions in this material. In both morphologies, we observe the presence of at least two different spin-dependent recombination processes. At room temperature and 10 K, polaron-pair recombination through weakly spin-spin coupled intermediate charge-carrier pair states is dominant, while at low temperatures, additional signatures of spin-dependent charge transport through the interaction of polarons with triplet excitons are seen in the half-field resonance of a triplet spin-1 species. This additional contribution arises since triplet lifetimes are increased at lower temperatures. We tentatively conclude that spectral broadening induced by hyperfine coupling is slightly weaker in the more ordered \ensuremath{\beta}-phase than in the glassy phase since protons are more evenly spaced, whereas broadening effects due to spin-orbit coupling, which impacts the distribution of $g$-factors, appear to be somewhat more significant in the \ensuremath{\beta}-phase.

Separating hyperfine from spin-orbit interactions in organic semiconductors by multi-octave magnetic resonance using coplanar waveguide microresonators

Separating the influence of hyperfine from spin-orbit interactions in spin-dependent carrier recombination and dissociation processes necessitates magnetic resonance spectroscopy over a wide range of frequencies. We have designed compact and versatile coplanar waveguide resonators for continuous-wave electrically detected magnetic resonance and tested these on organic light-emitting diodes. By exploiting both the fundamental and higher-harmonic modes of the resonators, we cover almost five octaves in resonance frequency within a single setup. The measurements with a common π-conjugated polymer as the active material reveal small but non-negligible effects of spin-orbit interactions, which give rise to a broadening of the magnetic resonance spectrum with increasing frequency.

Triplet excitons as sensitive spin probes for structure analysis of extended defects in microcrystalline silicon

Electrically detected magnetic resonance (EDMR) spectroscopy is employed to study the influence of triplet excitons on the photocurrent in state-of-the-art microcrystalline silicon thin-film solar cells. These triplet excitons are used as sensitive spin probes for the investigation of their electronic and nuclear environment in this mixed-phase material. According to low-temperature EDMR results obtained from solar cells with different $^{29}\mathrm{Si}$ isotope concentrations between $0.01%$ and $50%$, the triplet excitons reside at extended defects in the crystallites of microcrystalline silicon that give rise to shallow states in the silicon band gap. The excitons possess a rather delocalized wave function, couple to electron spins in conduction band tail states nearby, and take part in a spin-dependent recombination process. Our study shows that extended defects such as grain boundaries or stacking faults in the crystalline part of the material act as charge carrier traps that can influence the material conductivity.

Magnetic-field-induced photocurrent in metal-dielectric-semiconductor heterostructures based on cobalt nanoparticles SiO2(Co)/GaAs

Magnetic-field influence on photocurrent in heterostructures of silicon dioxide films with cobalt nanoparticles SiO2(Co) grown on gallium arsenide GaAs substrate has been studied in the avalanche regime at room temperature. High values of magnetic-field-induced photocurrent were found in the vicinity and above the GaAs bandgap of ∼1.4eV. For photon energies E>1.4eV the photocurrent significantly increases, while the avalanche process is suppressed by the magnetic field, and the current flowing through the heterostructure decreases. The photocurrent is enhanced in the SiO2(Co 60at%)/GaAs heterostructure at the magnetic field H=1.65kOe by factor of about 10 for the photon energy E=1.5eV. This phenomenon is explained by a model based on electronic transitions in magnetic fields with the spin-dependent recombination process at deep impurity centers in the SiO2(Co)/GaAs interface region.

Dramatic impact of the giant local magnetic fields on spin-dependent recombination processes in gadolinium based garnets

A giant magnetic field effect on spin-dependent recombination of the radiation-induced defects has been found in cerium doped gadolinium based garnet crystals and ceramics, promising materials for scintillator applications. A sharp and strong increase in the afterglow intensity stimulated by external magnetic field and an evidence of the magnetic field memory have been discovered. The effect was ascribed to huge Gd-induced internal magnetic fields, which suppress the recombination, and cross-relaxation with Gd3+ ions leading to reorientation of the spins of the electron and hole centers. Thus, the spin system of radiation-induced defects in gadolinium garnet based scintillator materials was shown to accumulate significant energy which can be released in external magnetic fields.

CW and pulsed electrically detected magnetic resonance spectroscopy at 263 GHz/12 T on operating amorphous silicon solar cells

Here we describe a new high frequency/high field continuous wave and pulsed electrically detected magnetic resonance (CW EDMR and pEDMR) setup, operating at 263GHz and resonance fields between 0 and 12T. Spin dependent transport in illuminated hydrogenated amorphous silicon p–i–n solar cells at 5K and 90K was studied by in operando 263GHz CW and pEDMR alongside complementary X-band CW EDMR. Benefiting from the superior resolution at 263GHz, we were able to better resolve EDMR signals originating from spin dependent hopping and recombination processes. 5K EDMR spectra were found to be dominated by conduction and valence band tail states involved in spin dependent hopping, with additional contributions from triplet exciton states. 90K EDMR spectra could be assigned to spin pair recombination involving conduction band tail states and dangling bonds as the dominating spin dependent transport process, with additional contributions from valence band tail and triplet exciton states.

Effect of magnetic field enhancement of the photocurrent in ferromagnetic metal-dielectric heterostructures SiO2(Co)/GaAs

Heterostructures of silicon dioxide films containing cobalt nanoparticles SiO2(Co) grown on GaAs substrate exhibit at room temperature high values of magnetic field enhancement of photocurrent in the vicinity and above the GaAs bandgap of ∼1.4 eV. For photon energies E above the GaAs bandgap, the photocurrent significantly increases, while the avalanche process is suppressed by the magnetic field, and the current flowing through the heterostructure decreases. The photocurrent is enhanced in the SiO2(Co 60 at. %)/GaAs heterostructure at the magnetic field H = 1.65 kOe by a factor of about ten for the photon energy E = 1.5 eV. This phenomenon is explained by a model describing electronic transitions in magnetic fields with the spin-dependent recombination process at deep impurity centers in the GaAs interface region.

Submillisecond hyperpolarization of nuclear spins in silicon.

In this Letter, we devise a fast and effective nuclear spin hyperpolarization scheme, which is, in principle, magnetic field independent. We use this scheme to experimentally demonstrate polarizations of up to 66% for phosphorus donor nuclear spins in bulk silicon, which are created within less than 100 μs in a magnetic field of 0.35T at a temperature of 5K. The polarization scheme is based on a spin-dependent recombination process via weakly coupled spin pairs, for which the recombination time constant strongly depends on the relative orientation of the two spins. We further use this scheme to measure the nuclear spin relaxation time and find a value of ∼100 ms under illumination, in good agreement with the value calculated for nuclear spin flips induced by repeated ionization and deionization processes.

Spin-dependent recombination and single charge dynamics in silicon nanostructrures

In this work we report on the investigation of spin-dependent recombination processes in silicon nanowires and of the single charge dynamics on a donor atom coupled to a quantum dot.

Spin-dependent recombination involving oxygen-vacancy complexes in silicon

Spin-dependent relaxation and recombination processes in $\gamma$-irradiated $n$-type Czochralski-grown silicon are studied using continuous wave (cw) and pulsed electrically detected magnetic resonance (EDMR). Two processes involving the SL1 center, the neutral excited triplet state of the oxygen-vacancy complex, are observed which can be separated by their different dynamics. One of the processes is the relaxation of the excited SL1 state to the ground state of the oxygen-vacancy complex, the other a charge transfer between $^{31}$P donors and SL1 centers forming close pairs, as indicated by electrically detected electron double resonance. For both processes, the recombination dynamics are studied with pulsed EDMR techniques. We demonstrate the feasibility of true zero-field cw and pulsed EDMR for spin 1 systems and use this to measure the lifetimes of the different spin states of SL1 also at vanishing external magnetic field.

Real-time electrical detection of coherent spin oscillations

We demonstrate that the bandwidth of pulsed electrically detected magnetic resonance can be increased to at least 80 MHz using a radio frequency-reflectometry detection scheme. Using this technique, we measure coherent spin oscillations in real time during a resonant microwave pulse. We find that the observed signal is in quantitative agreement with simulations based on rate equations modeling the recombination dynamics of the spin system under study. The increased bandwidth opens the way to electrically study faster spin-dependent recombination processes, e.g., in direct semiconductors which so far have almost exclusively been studied by optically detected magnetic resonance.

Time constants of spin-dependent recombination processes

We present experiments to systematically study the time constants of spin-dependent recombination processes in semiconductors using pulsed electrically detected magnetic resonance (EDMR). The combination of time-programmed optical excitation and pulsed spin manipulation allows us to directly measure the recombination time constants of electrons via localized spin pairs and the time constant of spin pair formation as a function of the optical excitation intensity. Using electron nuclear double resonance, we show that the time constant of spin pair formation is determined by an electron capture process. Based on these time constants we devise a set of rate equations to calculate the current transient after a resonant microwave pulse and compare the results with experimental data. Finally, we critically discuss the effects of different boxcar integration time intervals typically used to analyze pulsed EDMR experiments on the determination of the time constants. The experiments are performed on phosphorus-doped silicon, where EDMR via spin pairs formed by phosphorus donors and Si/SiO2 interface dangling bond defects is detected.

Shallow Donors and Deep-Level Color Centers in Bulk AlN Crystals: EPR, ENDOR, ODMR and Optical Studies

The results of studies of shallow donors and deep-level color centers in bulk AlN crystals are presented. Two shallow donors (presumably oxygen located on the nitrogen site and carbon located on the aluminum site) are suggested to exhibit the DX-relaxation. Third shallow donor (presumably silicon on the Al site) shows the shallow donor behavior up to the room temperature and can be observed without light excitation at temperatures above 200 K. The values of the Bohr radius of the shallow donors are estimated. The structure of deep-level color centers (neutral nitrogen vacancy VN) in bulk AlN crystals is determined and analyzed by electron paramagnetic resonance, electron-nuclear double resonance, optical absorption and thermoluminescence induced by X-ray irradiation. Spin-dependent recombination processes in AlN crystals are studied by means of optically detected magnetic resonance.

Efficient room-temperature spin detector based on GaNAs

Efficient and highly spin-dependent recombination processes are shown to not only turn GaNAs into an efficient spin filter but also to make it an excellent spin detector functional at room temperature (RT). By taking advantage of the defect-engineered spin-filtering effect, the spin detection efficiency is no longer limited by the fast spin relaxation of conduction electrons. This leads to a significant enhancement in the optical polarization of the spin detector, making it possible to reliably detect even very weak electron spin polarization at RT, as demonstrated by a study of spin loss during optical spin injection across a GaAs/GaNAs interface.

Effects of P implantation and post-implantation annealing on defect formation in ZnO

Photoluminescence (PL) and optically detected magnetic resonance (ODMR) techniques are utilized to examine the effects of P implantation and post-implantation annealing on defect formation in ZnO single crystals. From ODMR, the main defects created by ion implantation include oxygen and zinc vacancies as a well as a deep donor labeled as PD. The formation of the PD defect is likely promoted by the presence of P as it could only be detected in the P-containing ZnO. The VO and PD centers are found to exhibit low thermal stability and can be annealed out at 800 °C. On the other hand, a new set of defects, such as Z, T, and D* centers, is detected after annealing. Based on measured spectral dependences of the ODMR signals, the VO, VZn, and PD centers are shown to participate in spin-dependent recombination processes related to red emissions, whereas the Z, T, and D* centers are involved in radiative recombination over a wide spectral range of 1.55–2.5 eV. From the PL measurements, combined effects of implantation and annealing also lead to appearance of a new PL band peaking at ∼3.156 eV, likely due to donor-acceptor-pair recombination. The formation of the involved deep acceptor is concluded to be facilitated by the presence of P.

Nuclear Spins of Ionized Phosphorus Donors in Silicon

We demonstrate the coherent control and electrical readout of ionized phosphorus donor nuclear spins in (nat)Si. By combining time-programed optical excitation with coherent electron spin manipulation, we selectively ionize the donors depending on their nuclear spin state, exploiting a spin-dependent recombination process at the Si/SiO(2) interface, and find a nuclear spin coherence time of 18 ms for the ionized donors. The presented technique allows for spectroscopy of ionized-donor nuclear spins and enhances the sensitivity of electron nuclear double resonance to a level of 3000 nuclear spins.

Point defects in ZnO: Electron paramagnetic resonance study

Abstract The results of electron paramagnetic resonance (EPR), photo-EPR, and optical detection of EPR (ODEPR) investigation of different point defects in ZnO single crystals, ceramics and powders are reported. The main attention is given to EPR and photo-EPR studies of oxygen vacancy (VO) being in scope of many experimental and theoretical investigations. Different EPR and ODEPR spectra related to VO and reported in literature are analyzed and their temperature stability is investigated. The properties of the Pb atoms playing important role in spin dependent recombination process are studied. Specific features of the VO+ and Pb3+ EPR spectra, such as (i) reversal and not reversal change of EPR lines intensity under excitation by light with different wavelengths, (ii) fast increase followed by slow decrease of EPR spectra when light is switched on, (iii) correlation between EPR photoexcitation and persistent microwave photoconductivity are discussed. Spectral and time dependences of the Pb3+ EPR spectrum are explained taking into account double donor nature of Pb in ZnO. Experimental results on the photoexcitation and quench of the VO+ EPR spectrum in different ZnO samples are reported.

Electrically detected magnetic resonance of phosphorous due to spin dependent recombination with triplet centers in γ-irradiated silicon

Abstract Electrically detected magnetic resonance (EDMR) of phosphorus in silicon was detected in weak magnetic fields at low resonance frequencies of 200–400 MHz before and after irradiation of samples by γ-rays. EDMR spectra were detected by measuring dc-photoconductivity of samples under band-gap illumination. Phosphorus (P0) EDMR lines are accompanied always with the single line (S-line) with g-factor ≈2.01 originated most likely from the surface recombination centers. Strong, about 10 times, increase of the P0 and S signals was found in the same samples after irradiation with the doses of (3−6)×1015 γ/cm−2. For these doses of irradiation we were also able to see the ESR transition between entangled states of phosphorous formed at low magnetic field. This shows the higher efficiency of spin dependent recombination (SDR) process in irradiated samples. In addition, several new EDMR lines emerged after irradiation. Some of them arose from the spin dependent recombination through the photoexcited triplet states of A-centers (oxygen+vacancy complex).

Electron spin control in dilute nitride semiconductors

We report on a study of spin-dependent recombination processes (SDR)for conduction band electrons on deep paramagnetic centers in a series ofGaAs1−yNy epilayers by time-resolved optical orientation experiments. We demonstrate that thisdilute nitride compound can be used as an effective electron spin filter undera polarized optical excitation of appropriate intensity. This optimum intensitycan moreover be controlled by adjusting the nitrogen composition in the layer.