Silicon Divacancy Research Articles

Spin-Orbit Coupling of Color Centers for Quantum Applications

Color centers in 4H-SiC and diamond are candidates for single photon sources and qubits for the implementation of quantum applications. The CI-cRPA method is able to correctly reproduce the structure of the underlying highly correlated wave functions for low and high spin multiplets. Aiming for a more complete understanding of spin-orbit mediated intersystem crossing between such states, we have extended CI-cRPA by a first order treatment of the spin-orbit interactions. We present preliminary results for intercrossing matrix elements and contributions of spin-orbit coupling to the zero field splitting of the silicon vacancy and di-vacancy in 4H-SiC, as well as the NV center in diamond using this approach.

Formation and stability of point defect color centers in 6H silicon carbide

Point defect color centers acting as single-photon emitters are promising for quantum technology applications and have been extensively studied, e.g., in the 4H polytype of silicon carbide (SiC). However, the physics of such color centers in other SiC polytypes is much less explored. Herein, we study the formation and thermal stability of such color centers in 6H-SiC using photoluminescence spectroscopy. The emissions from typical single-photon emitters, such as silicon vacancies, divacancies, and carbon antisite-vacancy pairs in 6H-SiC, were monitored as a function of the proton irradiation fluence and post-irradiation annealing, and compared to that in 4H-SiC. Overall, at the background of similarities between the emission behavior in 4H- and 6H-SiC polytypes, we observed prominent differences; e.g., for the thermal stability of the carbon antisite-vacancy pair, which exhibited maximized emissions upon 300 and 900 °C anneals in 4H- and 6H-SiC, respectively. Moreover, we observed a range of defect emission signatures not previously reported for 6H-SiC in the literature and discussed their potential origin in the context of the thermal stability. For example, among the PL-lines in 6H-SiC, we detected periodically repeatable emission signatures, resembling the so-called L-lines recently reported in 4H-SiC, even though their exact origin has not yet been settled in the literature. Thus, we use color centers comparison in different polytypes to better understand the nature of the single-photon emitters in SiC.

Midgap state requirements for optically active quantum defects

Optically active quantum defects play an important role in quantum sensing, computing and communication. The electronic structure and the single-particle energy levels of these quantum defects in the semiconducting host have been used to understand their optoelectronic properties. Optical excitations that are central for their initialization and readout are linked to transitions between occupied and unoccupied single-particle states. It is commonly assumed that only quantum defects introducing levels well within the band gap and far from the band edges are of interest for quantum technologies as they mimic an isolated atom embedded in the host. In this perspective, we contradict this common assumption and show that optically active defects with energy levels close to the band edges can display similar properties. We highlight quantum defects that are excited through transitions to or from a band-like level (bound exciton) such as the T center and Se Si+ in silicon. We also present how defects such as the silicon split-vacancy in diamond can involve transitions between localized levels that are above the conduction band or below the valence band. Loosening the commonly assumed requirement on the electronic structure of quantum defects offers opportunities in quantum defects design and discovery especially in smaller band gap hosts such as silicon. We discuss the challenges in terms of operating temperature for photoluminescence or radiative lifetime in this regime. We also highlight how these alternative type of defects bring their own needs in terms of theoretical developments and fundamental understanding. This perspective clarifies the electronic structure requirement for quantum defects and will facilitate the identification and design of new color centers for quantum applications especially driven by first principles computations.

Formation of Paramagnetic Defects in the Synthesis of Silicon Carbide.

Silicon carbide (SiC) is a very promising platform for quantum information processing, as it can host room temperature solid state defect quantum bits. These room temperature quantum bits are realized by paramagnetic silicon vacancy and divacancy defects in SiC that are typically introduced by irradiation techniques. However, irradiation techniques often introduce unwanted defects near the target quantum bit defects that can be detrimental for the operation of quantum bits. Here, we demonstrate that by adding aluminum precursor to the silicon and carbon sources, quantum bit defects are created in the synthesis of SiC without any post treatments. We optimized the synthesis parameters to maximize the paramagnetic defect concentrations-including already established defect quantum bits-monitored by electron spin resonance spectroscopy.

To define nonradiative defects in semiconductors: An accurate DLTS simulation based on first-principle

Deep level transient spectroscopy (DLTS) is a crucial technique to characterize the defects in semiconductor devices. Within the framework of the state-of-the-art density functional theory (DFT), the simulation for experimental DLTS spectra is realized successfully with high accuracy and intrinsic physics in this work, of which the reliability is confirmed by nonlocal hybrid functional. The electron–phonon coupling is included to describe the thermal-activated behavior of the hot carrier nonradiative capture reflected by DLTS signal. In the case study, the divacancy in silicon is employed for the flow of DLTS calculation as a benchmark, of which the results are verified by our 40 MeV Si irradiation experiments on the NPN and PNP bipolar junction transistors and previous reports. The problem we can address is the identification of defect characterized in DLTS experiments. The realization of DLTS simulation would have a profound significance for understanding the underlying physics in experimental observations and be a powerful leverage to define defect nature in semiconductors.

Charge state control of the silicon vacancy and divacancy in silicon carbide

Color centers in silicon carbide (SiC), such as the negative silicon vacancy (VSi−) and neutral divacancy (VSiVC0), have recently been shown to be promising quantum bits (qubits) for a variety of applications in quantum communications and sensing. Considerable effort has been spent on improving the performance of these optical spin qubits, and the instability of their charge state is an important issue to be solved. Using electron paramagnetic resonance to monitor the charge state of dominant intrinsic defects in n-type, high-purity semi-insulating and p-type 4H-SiC, we reveal carrier compensation processes and the windows of the Fermi level that allow us to obtain stable VSi− and VSiVC0 in equilibrium. We show that stable VSi− and VSiVC0 ensembles can be obtained in n-type (p-type) via controlling the concentration of the Si vacancy (the C vacancy and the C antisite–vacancy pairs). The charge-state control of single VSi− and VSiVC0 emitters is expected to be possible in pure p-type layers by controlling the concentration of the C vacancy. In ultrapure materials, optical repumping is required for charge state control of single emitters.

Proton-induced traps in electron multiplying charge-coupled devices

Charge-coupled device (CCD)-based technologies exposed to high-energy radiation are susceptible to the formation of stable defects within the charge transfer channel that defer signal to subsequent pixels and limit the lifetime of the detector. Performance degradation due to these defects depends upon the interplay between the clock timings used to operate the device and the properties of defects introduced by irradiation. Characterization of both the type and number of post-irradiation defects makes it possible to minimize charge loss though the appropriate selection of clock timings for a given operating temperature. This technique has the potential to increase nominal mission lifetimes by several years for CCD-based instruments and is of particular significance to electron multiplying charge-coupled devices (EMCCDs) for photon counting applications where the effect of charge traps on low signal levels is expected to be most severe. We present a study of charge traps within CCDs, specifically within EMCCDs irradiated at room temperature to proton fluences up to and including 1.45 × 1010 p + / cm2 (74 MeV). Defects are characterized through the “single-trap pumping” technique, with clocking schemes specifically designed for the 2-phase pixel architecture of the EMCCD. Five dominant trap species are thought to be introduced by the irradiation, the Si-E center, Si-A center, double and single acceptor charge states of the silicon divacancy (VV − − , VV − ), and an as yet unidentified defect referred to here as the Si-U center (the “unknown” trap). Energy-level and cross-section values are presented that allow inference of the defect landscape for a range of proton fluences and operating temperatures. While the study focuses specifically on EMCCDs, in more general terms, the results for trap properties are interpreted as being applicable to all CCD types following irradiation and can serve as a foundation for future charge loss correction and optimization techniques.

Piezoresistance in Defect-Engineered Silicon

The steady-state, space-charge-limited piezoresistance (PZR) of defect-engineered, silicon-on-insulator device layers containing silicon divacancy defects changes sign as a function of applied bias. Above a punch-through voltage ($V_t$) corresponding to the onset of a space-charge-limited hole current, the longitudinal $\langle 110 \rangle$ PZR $\pi$-coefficient is $\pi \approx 65 \times 10^{-11}$~Pa$^{-1}$, similar to the value obtained in charge-neutral, p-type silicon. Below $V_t$, the mechanical stress dependence of the Shockley-Read-Hall (SRH) recombination parameters, specifically the divacancy trap energy $E_T$ which is estimated to vary by $\approx 30$~$\mu$V/MPa, yields $\pi \approx -25 \times 10^{-11}$~Pa$^{-1}$. The combination of space-charge-limited transport and defect engineering which significantly reduces SRH recombination lifetimes makes this work directly relevant to discussions of giant or anomalous PZR at small strains in nano-silicon whose characteristic dimension is larger than a few nanometers. In this limit the reduced electrostatic dimensionality lowers $V_t$ and amplifies space-charge-limited currents and efficient SRH recombination occurs via surface defects. The results reinforce the growing evidence that in steady state, electro-mechanically active defects can result in anomalous, but not giant, PZR.

The relationship between the doping concentration and d ferromagnetism in n-type 4H-SiC

To date, research on defect-induced magnetism in SiC has been conducted to clarify the relationship between the ferromagnetic signal and the carrier concentration. It has been experimentally proven that there is an interaction between the d0 magnetic moment and the hole carrier in p-type 4H-SiC. However, for n-type SiC, the existing theoretical predictions are insufficient to explain the variation in magnetization with the doping concentration. To solve this problem, we prepared 4H-SiC epitaxial layers with different nitrogen doping concentrations and introduced defects by ion implantation. By measuring and analyzing the magnetic properties, we found that the ferromagnetic composition depends on both the implantation dose and the doping concentration. By performing first-principles calculations, we studied the magnetic moments and interactions of defects with different charge states, which is related to defect-induced ferromagnetism. These defects include not only the paramagnetic centers reported in previous studies, such as silicon vacancies and divacancies, but also the NCVSi complex defect of recent interest, which are indicated by positron annihilation experiments. Combining experimental observations with theoretical calculations, we explained the relationship between magnetic properties and the nitrogen doping concentration in the epitaxial samples. Our research will help us to better understand the physical mechanism of defect-induced magnetism in doped semiconductors and provide a potential platform for the control of defect-induced magnetism by carrier density modulation and the fabrication of SiC spintronic devices without transition metals.

Effect of Isovalent Doping on Hydrogen Passivated Vacancy-oxygen Defect Complexes in Silicon: Insights from Density Functional Theory

Using the hybrid density functional theory (DFT) computational approach, we examine the effect of hydrogen passivation and isovalent doping on the vacancy(Vn)-oxygen interstitial(Oi), i.e., Vn-Omi (n, m = 0,1,2) defect complexes in silicon. Specifically, we study the structural properties, relative stability and defect levels induced by the V, V2, VOi, V2Oi VO2i defect complexes. We found that hydrogen passivation improve the electrical activity of silicon vacancy and divacancy, but has negative or undesirable effect on the electrical activity of VOi, V2Oi VO2i defect complexes. To remove the negative effect of hydrogen passivation, isovalent doping of VOi, V2Oi VO2i defect complexes with each of Ge, Sn and Pb is carried out. This is found to improve the electrical activity of the defect complexes by shifting the defect-induced acceptor and shallow donor levels deep into the valence and the conduction bands, respectively. Our work emphasizes the importance of isovalent doping in improving the electrical activity of silicon containing hydrogen and vacancy-oxygen defect complexes.

Deterministic placement of ultra-bright near-infrared color centers in arrays of silicon carbide micropillars.

We report the enhancement of the optical emission between 850 and 1400 nm of an ensemble of silicon mono-vacancies (VSi), silicon and carbon divacancies (VCVSi), and nitrogen vacancies (NCVSi) in an n-type 4H-SiC array of micropillars. The micropillars have a length of ca. 4.5 μm and a diameter of ca. 740 nm, and were implanted with H+ ions to produce an ensemble of color centers at a depth of approximately 2 μm. The samples were in part annealed at different temperatures (750 and 900 °C) to selectively produce distinct color centers. For all these color centers we saw an enhancement of the photostable fluorescence emission of at least a factor of 6 using micro-photoluminescence systems. Using custom confocal microscopy setups, we characterized the emission of VSi measuring an enhancement by up to a factor of 20, and of NCVSi with an enhancement up to a factor of 7. The experimental results are supported by finite element method simulations. Our study provides the pathway for device design and fabrication with an integrated ultra-bright ensemble of VSi and NCVSi for in vivo imaging and sensing in the infrared.

Моделирование областей разупорядочения в процессе радиационного дефектообразования

This article discusses the model of regions of disordering that are formed as a result of the separation of Frenkel pairs, taking into account the neutral and charged state of the pair. The probability of separation depends on the temperature and the position of the Fermi level in the band gap, therefore, the concentration of primary radiation defects also depends on the temperature and concentrations of donors, acceptors. The depth distribution profiles of primary radiation defects created by low-energy protons in silicon and the dependence of the parameters of the disordering regions on the proton energy are calculated. It is shown that the maximum of the distribution of the disordering regions created by protons is always spatially separated from the maxima of the interstitial silicon distribution, vacancies and divacancies, which allows changing the surface and volume properties of semiconductor structures in various ways. The results obtained are used to predict the characteristics of semiconductor devices operating under conditions of radiation exposure.

Interaction between the divacancy and hydrogen in silicon: Observation of fast and slow kinetics

The divacancy (V2) is one of the fundamental defects in silicon. However, the interaction of V2 with hydrogen is still not fully understood. In the present work, deep level transient spectroscopy (DLTS) results on hydrogen-assisted annealing of V2 are presented. H+ ions were implanted with multiple energies into n-type Czochralski-grown samples, yielding uniform (box-like) concentration-versus-depth profiles of V2 and hydrogen in the region probed by the DLTS measurements. The evolution kinetics of V2 reveals two distinct processes: (i) a fast one attributed to dissociation of phosphorus-hydrogen pairs and reaction with highly mobile atomic Hi and (ii) a slow one whose origin is not identified yet. During the slow process, we observe the formation of a hydrogen-related electronic state, labeled E5* and positioned ∼0.42 eV below the conduction band edge. The growth of E5* displays a close one-to-one proportionality with the loss of a V2-related DLTS peak, presumably due to V2H, overlapping with that of the single negatively charged V2.

Development of in-situ trap characterisation techniques for EMCCDs

The “trap pumping” technique has seen considerable use over recent years as a means to probe the intrinsic properties of silicon defects that can impact charge transfer performance within CCD-based technologies. While the theory behind the technique is reasonably well understood, it has to date only been applied to relatively simple pixel designs where the motion of charge between pixel phases is fairly easy to predict. For some devices, the intrinsic pixel architecture is more complex and can consist of unequal phase sizes and additional implants that deform the electronic potential. Here, we present the implementation of the trap pumping technique for the CCD201-20, a 2-phase Teledyne e2v EMCCD. Clocking schemes are presented that can provide the location of silicon defects to sub-micron resolution. Experimental techniques that allow determination of trap energy levels and emission cross sections are presented. These are then implemented on an irradiated CCD201-20 to determine the energy level and emission cross section for defects thought to be the double acceptor state of the silicon divacancy (VV−−) and carbon-phosphorus (CiPs) pairs. An improvement in charge transfer performance through optimised parallel clock delay is demonstrated and found to correlate with the properties of defects found using the trap pumping technique.

Evolution and Impact of Defects in a p-Channel CCD After Cryogenic Proton-Irradiation

The p-channel charge coupled devices (CCDs) have been shown to display improved tolerance to radiation-induced charge transfer inefficiency when compared with n-channel CCDs. However, the defect distribution formed during irradiation is expected to be temperature dependent due to the differences in lattice energy caused by a temperature change. This has been tested through defect analysis of two p-channel e2v CCD204 devices, one irradiated at room temperature and one at a cryogenic temperature (153 K). Analysis is performed using the method of single trap pumping. The dominant charge trapping defects at these conditions have been identified as the donor level of the silicon divacancy and the carbon interstitial defect. The defect parameters are analyzed both immediately postirradiation and following several subsequent room-temperature anneal phases up until a cumulative anneal time of approximately 10 months. We have also simulated charge transfer in an irradiated CCD pixel using the defect distribution from both the room-temperature and cryogenic case, to study how the changes affect imaging performance. The results demonstrate the importance of cryogenic irradiation and annealing studies, with large variations seen in the defect distribution when compared to a device irradiated at room-temperature, which is the current standard procedure for radiation-tolerance testing.

In situ trap properties in CCDs: the donor level of the silicon divacancy

The silicon divacancy is one of the main defects of concern in radiation damage studies of Charge-Coupled Devices (CCDs) and, being immobile at room temperature, the defect is accessible to a variety of characterisation techniques. As such, there is a large amount of (often conflicting) information in the literature regarding this defect. Here we study the donor level of the divacancy, one of three energy levels which lie between the silicon valence and conduction bands. The donor level of the divacancy acts as a trap for holes in silicon and therefore can be studied through the use of a p-channel CCD. The method of trap-pumping, linked closely to the process of pocket-pumping, has been demonstrated in the literature over the last two years to allow for in-situ analysis of defects in the silicon of CCDs. However, most work so far has been a demonstartion of the techinique. We begin here to use the technique for detailed studies of a specific defect centre in silicon, the donor level of the divacancy. The trap density post-irradiation can be found, and each instance of the trap identified independently of all others. Through the study of the trap response at different clocking frequencies one can measure directly the defect emission time constant, and through tracking this at different temperatures, it is possible to use Shockley-Read-Hall theory to calculate the trap energy level and cross-section. A large population of traps, all with parameters consistent with the donor level of the divacancy, has been studied, leading to a measure of the distribution of properties. The emission time constant, energy level and cross-section are found to have relatively large spreads, significantly beyond the small uncertainty in the measurement technique. This spread has major implications on the correction of charge transfer inefficiency effects in space applications in which high precision is required.

Mechanisms for optical loss in SOI waveguides for mid-infrared wavelengths around 2 μm

We report the measurement of optical loss in submicron silicon-on-insulator waveguides at a wavelength of 2.02 μm for the fundamental TE mode. Devices were fabricated at IMEC and at A⋆STAR's Institute of Microelectronics (IME) and thus these measurements are applicable to studies which require fabrication using standard foundry technology. Propagation loss for strip and rib waveguides of 3.3 ± 0.5 and 1.9 ± 0.2 dB cm−1 were measured. Waveguide bending loss in strip and rib waveguides was measured to be 0.36 and 0.68 dB per 90° bend for a radius of 3 μm. Doped waveguide loss in rib waveguides was measured for both n-type and p-type species at two doping densities for each doping type. Measured results from propagation, bending, and free-carrier loss were found to be in good agreement with analytical or numerical models. Loss due to lattice defects introduced by ion-implantation is found to be underestimated by a previously proposed empirical model. The thermal annealing of the lattice defects is consistent with removal of the silicon divacancy.

Spin-photon entanglement interfaces in silicon carbide defect centers

Optically active spins in solid-state systems can be engineered to emit photons that are entangled with the spin in the solid. This allows for applications such as quantum communications, quantum key distribution, and distributed quantum computing. Recently, there has been a strong interest in silicon carbide defects, as they emit very close to the telecommunication wavelength, making them excellent candidates for long range quantum communications. In this work we develop explicit schemes for spin-photon entanglement in several SiC defects: the silicon monovacancy, the silicon divacancy, and the NV center in SiC. Distinct approaches are given for (i) single-photon and spin entanglement and (ii) the generation of long strings of entangled photons. The latter are known as cluster states and comprise a resource for measurement-based quantum information processing.

Vacancy induced Jahn–Teller distortion in silicon and its influence to the electronic structure

Atomic and electronic structures of monovacancy (V1), divacancy (V2) and ring hexavacancy (V6) in crystalline silicon are studied using first-principles calculations in periodic supercells. Our results show that the V6 defect is the most stable among V1, V2 and V6 defects, and the V2-RB structure is a little more stable than the V2-LP structure due to lower vacancy formation energy. Furthermore, it is found that both V1 and V2 undergo the Jahn–Teller (JT) distortion while V6 does not. As a result, V1 and V2 have deep levels in the gap which mainly come from the neighboring atoms to vacancy. V6 has tailing bands in the gap, and so has a more stable electronic structure than V1 and V2. In addition, the JT distortion also reflects in the band decomposed charge density and the difference charge density.

Defects induced ferromagnetism in hydrogen irradiated 3C–SiC thin films

3C–SiC thin films are irradiated by hydrogen ions and its magnetic properties are studied experimentally. The magnetic and structural properties are characterized before and after hydrogen ions irradiation. The magnetic characterizations show that hydrogen ions irradiated 3C–SiC thin films displays room-temperature ferromagnetic behaviors. Micro-Raman spectrum reveals that hydrogen ions irradiation doesn’t change the crystal polytype or cause secondary phase. Photoluminescence characterization indicates that the main defects are silicon vacancies and divacancies. The defect concentration is obviously increased after hydrogen ions irradiation. The observed ferromagnetism in 3C–SiC thin films is attributed to silicon vacancies and divacancies induced by hydrogen ions irradiation.