We study the coupling of Pb0 dangling bond defects at the Si/SiO2 interface and 31P donors in an epitaxial layer directly underneath using electrically detected double electron-electron resonance (EDDEER). An exponential decay of the EDDEER signal is observed, which is attributed to a broad distribution of exchange coupling strengths J/2pi from 25 kHz to 3 MHz. Comparison of the experimental data with a numerical simulation of the exchange coupling shows that this range of coupling strengths corresponds to 31P-Pb0 distances ranging from 14 nm to 20 nm.
Electrically detected magnetic resonance (EDMR) is applied to mm size devices with implanted leads and a 50 micron square gap laid down on bulk phosphorus doped silicon. Devices with a range of phosphorus concentrations and surface types were prepared and measured to examine the interplay between donor and charge trap states in producing EDMR signals.
We investigate the spin species relevant for the spin-dependent recombination used for the electrical readout of coherent spin manipulation in phosphorus-doped silicon. Via a multi-frequency pump-probe experiment in pulsed electrically detected magnetic resonance, we demonstrate that the dominant spin-dependent recombination transition occurs between phosphorus donors and Si/SiO2 interface states. Combining pulses at different microwave frequencies allows us to selectively address the two spin subsystems participating in the recombination process and to coherently manipulate and detect the rel…
We report electrically detected magnetic resonance of phosphorus donors in a silicon field-effect transistor. An on-chip transmission line is used to generate the oscillating magnetic field allowing broadband operation. At milli-kelvin temperatures, continuous wave spectra were obtained up to 40 GHz, using both magnetic field and microwave frequency modulation. The spectra reveal the hyperfine-split electron spin resonances characteristic for Si:P and a central feature which displays the fingerprint of spin-spin scattering in the two-dimensional electron gas.
Exchange interactions among defects in semiconductors are commonly treated within effective-mass theory using a scaled hydrogenic wave-function. However such a wave-function is only applicable to shallow impurities; here we present a simple but robust generalization to treat deep donors, in which we treat the long-range part of the wavefunction using the well established quantum defect theory, and include a model central-cell correction to fix the bound-state eigenvalue at the experimentally observed value. This allows us to compute the effect of binding energy on exchange interactions as a fu…
Thermally activated delayed fluorescence (TADF) emitters consisting of donor and acceptor molecules are potentially highly interesting for electroluminescence (EL) applications. Their strong fluorescence emission is considered to be due to reverse intersystem crossing (RISC), in which energetically close triplet and singlet charge transfer (CT) states, also called exciplex states, are involved. In order to distinguish between different mechanisms and excited states involved, temperature-dependent spin-sensitive measurements on organic light-emitting diodes (OLEDs) and thin films are essential.…
We report measurements of spin-dependent scattering of conduction electrons by neutral donors in an accumulation-mode field-effect transistor formed in isotopically enriched silicon. Spin-dependent scattering was detected using electrically detected magnetic resonance where the spectra show resonant changes in the source-drain voltage for conduction electrons and electrons bound to donors. We discuss the utilization of spin-dependent scattering as a mechanism for the readout of donor spin-states in silicon based quantum computers.
Spin-dependent transport processes in thin near-surface doping regions created by low energy ion implantation of arsenic in silicon are detected by two methods, spin-dependent recombination (SDR) using microwave photoconductivity and electrically detected magnetic resonance (EDMR) monitoring the DC current through the sample. The high sensitivity of these techniques allows the observation of the magnetic resonance in particular of As in weak magnetic fields and at low resonance frequencies (40-1200 MHz), where high-field-forbidden transitions between the magnetic substates can be observed due …
We apply hybrid density functional theory calculations to identify the formation energies and thermodynamic charge transition levels of native point defects, common impurities, and shallow dopants in BAs. We find that boron-related defects such as V_B, B_As, B_i-V_B complexes, and antisite pairs are the dominant intrinsic defects. Native BAs is expected to exhibit p-type conduction due to the acceptor-type characteristics of V_B and B_As. Among the common impurities we explored, we found that C substitutional defects and H interstitials have relatively low formation energies and are likely to …
A study of donor electron spins and spin--dependent electronic transitions involving phosphorous ($^{31}$P) atoms in proximity of the (111) oriented crystalline silicon (c-Si) to silicon dioxide (SiO$_{2}$) interface is presented for [$^{31}$P] = 10$^{15}$ $\mathrm{cm}^{-3}$ and [$^{31}$P] = 10$^{16}$ $\mathrm{cm}^{-3}$ at about liquid $^4$He temperatures ($T = 5$ $\mathrm{K} - 15$ $\mathrm{K}$). Using pulsed electrically detected magnetic resonance (pEDMR), spin--dependent transitions between the \Phos donor state and two distinguishable interface states are observed, namely (i) \Pb centers w…
Zinc tin nitride (ZnSnN2) is attracting growing interest as a non-toxic and earth-abundant photoabsorber for thin-film photovoltaics. Carrier transport in ZnSnN2 and consequently cell performance are strongly affected by point defects with deep levels acting as carrier recombination centers. In this study, the point defects in ZnSnN2 are revisited by careful first-principles modeling based on recent experimental and theoretical findings. It is shown that ZnSnN2 does not have low-energy defects with deep levels, in contrast to previously reported results. Therefore, ZnSnN2 is more promising as …
The hyperfine interaction of phosphorus donors in fully strained Si thin films grown on virtual Si$_{1-x}$Ge$_x$ substrates with $x\leq 0.3$ is determined via electrically detected magnetic resonance. For highly strained epilayers, hyperfine interactions as low as 0.8 mT are observed, significantly below the limit predicted by valley repopulation. Within a Green's function approach, density functional theory (DFT) shows that the additional reduction is caused by the volume increase of the unit cell and a local relaxation of the Si ligands of the P donor.
We demonstrate the coherent control and electrical readout of the nuclear spins of ionized phosphorus donors in natural silicon. By combining pulsed illumination with coherent electron spin manipulation, we selectively ionize the donor depending on its nuclear spin state, exploiting a spin-dependent recombination process via a spin pair at the Si/SiO2 interface. The nuclear-spin coherence time of the ionized donor is 18 ms, two orders of magnitude longer than in the neutral donor state, rendering the ionized donor a potential resource as a quantum memory. The presented experimental techniques …
Magnetic field dependent polarization selective photoluminescence(PL) study has been carried out at 1.5~K on Gd-doped GaN epitaxial layers grown on c-SiC substrates by molecular beam epitaxy technique. It has been found that the incorporation of Gd in GaN leads to the generation of three types of donor like defects that result in neutral donor bound excitonic features in low temperature PL. The study reveals that the rate of spin-flip scattering for all the three excitonic features becomes almost $B$-independent suggesting that these signals must be stemming from defects which are ferromagneti…
The properties of ferroelectric materials, such as lead zirconate titanate (PZT), are heavily influenced by the interaction of defects with domain walls. These defects are either intrinsic, or are induced by the addition of dopants. We study here PbTiO$_3$ (the end member of a key family of solid solutions) in the presence of acceptor (Fe) and donor (Nb) dopants, and the interactions of the different defects and defect associates with the domain walls. For the case iron acceptors, the calculations point to the formation of defect associates involving an iron substitutional defect and a charged…
We present the results of electrically-detected magnetic resonance (EDMR) experiments on silicon with ion-implanted phosphorus nanostructures, performed at 5 K. The devices consist of high-dose implanted metallic leads with a square gap, into which Phosphorus is implanted at a non-metallic dose corresponding to 10^17 cm^-3. By restricting this secondary implant to a 100 nm x 100 nm region, the EDMR signal from less than 100 donors is detected. This technique provides a pathway to the study of single donor spins in semiconductors, which is relevant to a number of proposals for quantum informati…
Electrically detected magnetic resonance of $^{75}$As magnetic clock transitions in silicon
University of Melbourne（墨尔本大学）；University of Manchester（曼彻斯特大学）；University College London（伦敦大学学院）；RMIT University（皇家墨尔本理工大学）；Australian Research Council Centre for Quantum Computation and Communication Technology（澳大利亚研究委员会量子计算与通信技术中心）；CSIRO（联邦科学与工业研究组织）
Using first-principles method within the framework of the density functional theory, we study the influence of native point defect on the structural and electronic properties of Bi$_2$Se$_3$. Se vacancy in Bi$_2$Se$_3$ is a double donor, and Bi vacancy is a triple acceptor. Se antisite (Se$_{Bi}$) is always an active donor in the system because its donor level ($\varepsilon$(+1/0)) enters into the conduction band. Interestingly, Bi antisite(Bi$_{Se1}$) in Bi$_2$Se$_3$ is an amphoteric dopant, acting as a donor when $μ$$_e$$<$0.119eV (the material is typical p-type) and as an acceptor when $μ$$…
The semiconducting behaviour and optoelectronic response of gallium nitride is governed by point defect processes, which, despite many years of research, remain poorly understood. The key difficulty in the description of the dominant charged defects is determining a consistent position of the corresponding defect levels, which is difficult to derive using standard supercell calculations. In a complementary approach, we take advantage of the embedded cluster methodology that provides direct access to a common zero of the electrostatic potential for all point defects in all charge states. Charge…
Carbon doping is used to obtain semi-insulating GaN crystals. If the carbon doping concentration exceeds $5*10^{17}$ $cm^{-3}$, the carbon atoms increasingly form triatomic clusters. The tri-carbon defect structure is unambiguously proven by the isotope effect on the defects' local vibrational modes (LVMs) originally found in samples containing carbon of natural isotopic composition $(~99 $%$ ^{12}C, ~1$%$ ^{13}C)$ at $1679$ $cm^{-1}$ and $1718$ $cm^{-1}$. Number, spectral positions, and intensities of the LVMs for samples enriched with the $^{13}C$ isotope (~99 % and ~50 %) are consistently i…
From state-of-the-art density-functional calculations using hybrid functionals we show that, persistent $n$-type conductivity in ZnO is due to defect complexes formed between H with intrinsic and extrinsic defects. H exhibits cationic, anionic, and electrically-inactive character on interacting with defects in ZnO. The electrically-inactive molecular hydrogen can contribute to $n$-type conductivity in ZnO by activating deep donor levels into shallow levels. By calculating local vibrational mode frequencies, we have identified origins of many H-related Raman and infra-red frequencies and thus c…
Using hybrid density functional theory, we investigated formation energies and transition energies of possible donor-like defects in GaInO3, with the aim of exploring the sources of the experimentally observed n-type conductivity in this material. We predicted that O vacancies are deep donors; interstitial Ga and In are shallow donors but with rather high formation energies (>2.5 eV). Thus these intrinsic defects cannot cause high levels of n-type conductivity. However, ubiquitous H impurities existing in samples can act as shallow donors. As for extrinsic dopants, substitutional Sn and Ge are…
We present an analysis of gated InGaAs/InAlAs heterostructures, a device platform to realize spinorbitronic functionalities in semiconductors. The phenomenological model deduced from our magnetotransport experiments allows us to correlate the gate response of the studied two-dimensional electron systems to heterostructure design parameters, in particular the indium concentration. We explain the occurrence of metastable electrostatic configurations showing reduced capacitive coupling and provide gate operation strategies to reach classical field effect control in such heterostructures. Our stud…
Using silicon MOSFETs with thin (5nm) thermally grown SiO2 gate dielectrics, we characterize the density of electrically active traps at low-temperature after 16keV phosphorus ion-implantation through the oxide. We find that, after rapid thermal annealing at 1000oC for 5 seconds, each implanted P ion contributes an additional 0.08 plus/minus 0.03 electrically active traps, whilst no increase in the number of traps is seen for comparable silicon implants. This result shows that the additional traps are ionized P donors, and not damage due to the implantation process. We also find, using the roo…
SiC based metal-oxide-semiconductor field-effect transistors (MOSFETs) have gained a significant importance in power electronics applications. However, electrically active defects at the SiC/SiO$_2$ interface degrade the ideal behavior of the devices. The relevant microscopic defects can be identified by electron paramagnetic resonance (EPR) or electrically detected magnetic resonance (EDMR). This helps to decide which changes to the fabrication process will likely lead to further increases of device performance and reliability. EDMR measurements have shown very similar dominant hyperfine (HF)…
We report first-principles microscopic calculations of the formation energy, electrical activity, and magnetic moment of Co dopants and a variety of native defects in TiO2 anatase. Using these results, we use equilibrium thermodynamics to predict the resulting carrier concentration, the average magnetic moment per Co, and the dominant oxidation state of Co. The predicted values are in good agreement with experiment under the assumption of O-poor growth conditions. In this regime, a substantial fraction of Co dopants occupy interstitial sites as donors. The incomplete compensation of these dono…
Combined with magnetotransport measurements and first-principles calculations, we systematically investigated the effects of Bi incorporation on the electrical properties of the undoped InP1-xBix epilayers with 0<x<2.41%. The Hall-bar measurements reveal a dominant n-type conductivity of the InPBi samples. The electron concentrations are found to decrease firstly as x increases up to x=1.83%, and then increase again with further increasing Bi composition, whiles the electron mobility shows an inverse variation to the electron concentration. First-principle calculations suggest that both the ph…
Single photon sources are required for a wide range of applications in quantum information science, quantum cryptography and quantum communications. However, so far majority of room temperature emitters are only excited optically, which limits their proper integration into scalable devices. In this work, we overcome this limitation and present room temperature electrically triggered light emission from localized defects in zinc oxide (ZnO) nanoparticles and thin films. The devices emit at the red spectral range and show excellent rectifying behavior. The emission is stable over an extensive pe…
A method of the mid-IR-laser microscopy has been proposed for the investigation of the large-scale electrically and recombination active defects in semiconductors and non-destructive inspection of semiconductor materials and structures in the industries of microelectronics and photovoltaics. The basis for this development was laid with a wide cycle of the investigations on the low-angle mid-IR-light scattering in semiconductors. The essence of the technical idea was to apply the dark-field method for spatial filtering of the scattered light in the scanning mid-IR-laser microscope. This approac…
We present electrically detected electron nuclear double resonance measurements of the nuclear spins of ionized and neutral arsenic donors in strained silicon. In addition to a reduction of the hyperfine coupling, we find significant quadrupole interactions of the nuclear spin of the neutral donors of the order of 10 kHz. By comparing these to the quadrupole shifts due to crystal fields measured for the ionized donors, we identify the effect of the additional electron on the electric field gradient at the nucleus. This extra component is expected to be caused by the coupling to electric field …
We demonstrate radio frequency (RF) readout of electrically detected magnetic resonance in phosphorus-doped silicon metal-oxide field-effecttransistors (MOSFETs), operated at liquid helium temperatures. For the first time, the Si:P hyperfine lines have been observed using radio frequency reflectometry, which is promising for high-bandwidth operation and possibly time-resolved detection of spin resonance in donor-based semiconductor devices. Here we present the effect of microwave (MW) power and MOSFET biasing conditions on the EDMR signals.
This work reports an ESR study of low energy, low fluence phosphorus ion implantation into silicon in order to observe the activation of phosphorus donors placed in close proximity to the Si-SiO2 interface. Electrical measurements, which were used to estimate donor activation levels, reported high implant recoveries when using 14 keV phosphorus ions however, it was not possible to correlate the intensity of the hyperfine resonance signal with the electrical measurements in the presence of an SiO2 interface due to donor state ionisation (i.e. compensation effects). Comparative measurements made…
We present a theoretical description of the influence of misfit strain on mobile defects dynamics in thin strained ferroelectric films. Self-consistent solutions obtained by coupling the Poissons equation for electric potential with continuity equations for mobile donor and electron concentrations and time-dependent Landau-Ginzburg-Devonshire equations reveal that the Vegard mechanism (chemical pressure) leads to the redistribution of both charged and electro-neutral defects in order to decrease the effective stress in the film. Internal electric fields, both built-in and depolarization ones, …
The discovery of conducting two-dimensional electron gas (2DEG) and magnetism at the interface between insulating nonmagnetic oxides, as exemplified by the polar LaAlO3 and nonpolar SrTiO3 has raised prospects for attaining interfacial functionalities absent in the component materials. Yet, the microscopic origin of such emergent phenomena remains unclear, posing obstacles to design of improved functionalities. Using first principles defect calculations, we reveal a unifying polarity-induced defect mechanism for both conductivity and magnetism at polar-nonpolar interfaces of nonmagnetic insula…
Zinc sulfide (ZnS) based materials are widely used in many applications. Yet, due to a lack of detailed knowledge of defect energy levels, the electrical properties and luminescence mechanisms in the materials still give rise to debate. Here, we report a first-principles study of native point defects and impurities in zincblende ZnS using hybrid density-functional calculations. We find that cation and anion vacancies and antisite defects introduce deep defect levels in the band gap and can act as donors or acceptors depending on the position of the Fermi level. The substitutional impurity Cu$_…
Excited states of a single donor in bulk silicon have previously been studied extensively based on effective mass theory. However, a proper theoretical description of the excited states of a donor cluster is still scarce. Here we study the excitations of lines of defects within a single-valley spherical band approximation, thus mapping the problem to a scaled hydrogen atom array. A series of detailed full configuration-interaction and time-dependent hybrid density-functional theory calculations have been performed to understand linear clusters of up to 10 donors. Our studies illustrate the gen…
We have performed continuous wave and pulsed electron spin resonance measurements of implanted bismuth donors in isotopically enriched silicon-28. Donors are electrically activated via thermal annealing with minimal diffusion. Damage from bismuth ion implantation is repaired during thermal annealing as evidenced by narrow spin resonance linewidths (B_pp=12uT and long spin coherence times T_2=0.7ms, at temperature T=8K). The results qualify ion implanted bismuth as a promising candidate for spin qubit integration in silicon.
Using first-principles calculations, we explored all the 21 defect-pairs in GaN and considered 6 configurations with different defect-defect distances for each defect-pair. 15 defect-pairs with short defect-defect distances are found to be stable during structural relaxation, so they can exist in the GaN lattice once formed during the irradiation of high-energy particles. 9 defect-pairs have formation energies lower than 10 eV in the neutral state. The vacancy-pair VN-VN is found to have very low formation energies, as low as 0 eV in p-type and Ga-rich GaN, and act as efficient donors producin…
We report on low temperature photoluminescence (PL) and EPR study of bulk polycrystalline ZnO . Variation of peak position of donor bound exciton transition (D1XA) and FXAn=1-1LO with pump intensity show red shift and blue shift respectively due to exciton-exciton scattering. EPR spectra reveals three peaks at g value of 1.985, 1.956 and 1.939 respectively, g=1.956 and g=1.985 is due to shallow donors Zn interstitial and oxygen vacancy respectively An EPR spectrum at 100 K reveals higher degree of asymmetry and hyperfine splitting due to crystal field and inhomogeneous relaxation of paramagnet…
We demonstrate that the spin of optically addressable point defects can be coherently driven with AC electric fields. Based on magnetic-dipole forbidden spin transitions, this scheme enables spatially confined spin control, the imaging of high-frequency electric fields, and the characterization of defect spin multiplicity. While we control defects in SiC, these methods apply to spin systems in many semiconductors, including the nitrogen-vacancy center in diamond. Electrically driven spin resonance offers a viable route towards scalable quantum control of electron spins in a dense array.
Using hybrid density functional theory, we address point defects susceptible to cause charge compensation upon Mg doping of GaN. We determine the free energy of formation of the nitrogen vacancy and of several Mg-related defects. The entropic contribution as a function of temperature is determined within the quasiharmonic approximation. We find that the Mg interstitial shows a noticeably lower free energy of formation than the Mg substitutional to Ga in p-type conditions. Therefore, the Mg impurity is amphoteric behaving like an acceptor when substitutional to Ga and like a double donor when a…
Growth-controlled suppression of electrically active defects in CrSBr
Massachusetts Institute of Technology（麻省理工学院）；Wellesley College（韦尔斯利学院）；Bielefeld University（比勒费尔德大学）；Radboud University（拉德堡德大学）；University of Chemistry and Technology Prague（布拉格化工大学）
We investigate the role of transition metal atoms of group V-b (V, Nb, and Ta) and VI-b (Cr, Mo, and W) as n- or p-type dopants in anatase TiO2 using thermodynamic principles and density functional theory with the Heyd-Scuseria-Ernzerhof HSE06 hybrid functional. The HSE06 functional provides a realistic value for the band gap, which ensures a correct classification of dopants as shallow or deep donors or acceptors. Defect formation energies and thermodynamic transition levels are calculated taking into account the constraints imposed by the stability of TiO2 and the solubility limit of the imp…
Modulation of donor electron wavefunction via electric fields is vital to quantum computing architectures based on donor spins in silicon. For practical and scalable applications, the donor-based qubits must retain sufficiently long coherence times in any realistic experimental conditions. Here, we present pulsed electron spin resonance studies on the longitudinal $(T_1)$ and transverse $(T_2)$ relaxation times of phosphorus donors in bulk silicon with various electric field strengths up to near avalanche breakdown in high magnetic fields of about 1.2 T and low temperatures of about 8 K. We fi…
The negatively charged nitrogen-vacancy defect (NV)$^-$ in diamond has attracted much attention in recent years in qubit and biological applications. The negative charge is donated from nearby nitrogen donors that could limit or stem the successful application of (NV)$^-$. In this Letter, we unambiguously identify the \emph{neutral} nitrogen-vacancy defect (NV$^0$) by \emph{ab initio} supercell calculations. Our analysis shows that i) the spin state can be \emph{selectively} occupied optically, ii) the electron spin state can be manipulated by time-varying magnetic field, and iii) the spin sta…
We introduce a first-principles study to clarify the carrier-scattering property at the SiC/SiO$_2$. Interestingly, the electron transport at the conduction-band edge is significantly affected by the introduction of oxygen, even though there are no electrically active defects. The origin of the large scattering is explained by the behavior of the internal-space states (ISSs). Moreover, the effect of the ISSs is larger than that of the electrically active carbon-related defects. This result indicates that an additional scattering not considered in a conventional Si/SiO$_2$ occurs at the SiC/SiO…
Electrically and optically active charge carrier traps in silicon-doped few-layer GaSe
Walter-Schottky-Institut and TUM School of Natural Sciences, Technische Universität München（慕尼黑工业大学瓦尔特-肖特基研究所与自然科学学院）；Max Planck Institute for Chemical Physics of Solids（马克斯·普朗克固体化学物理研究所）；Department of Chemistry, Ludwig-Maximilians-Universität München（慕尼黑大学化学系）；Department of Inorganic Chemistry, University of Chemistry and Technology Prague（布拉格化工大学无机化学系）；School of Materials Science and Engineering, Jilin University（吉林大学材料科学与工程学院）；Institute of Physics and Astronomy, Technical University Berlin（柏林工业大学物理与天文研究所）
We present a variational method to calculate the exchange interactions among donor clusters in a semiconductor. Such clusters are candidates for a so-called control-qubit architecture for quantum information, where the effective exchange coupling between two atoms is controlled by the electronic state of a third. We use a combination of the effective-mass approximation and the quantum defect method; our variational ansatz is particularly suited to cases where an excited state of one of the donors (control) is partially delocalised over several different centres, forming an analogue of an exten…
We present the design and implementation of a scanning probe microscope, which combines electrically detected magnetic resonance (EDMR) and (photo-)conductive atomic force microscopy ((p)cAFM). The integration of a 3-loop 2-gap X-band microwave resonator into an AFM allows the use of conductive AFM tips as a movable contact for EDMR experiments. The optical readout of the AFM cantilever is based on an infrared laser to avoid disturbances of current measurements by absorption of straylight of the detection laser. Using amorphous silicon thin film samples with varying defect densities, the capab…
