Carbon-related Defects Research Articles

Spectrum of Tunneling Transport through Phonon-Coupled Defect States in a Carbon-Doped Hexagonal Boron Nitride Barrier.

Defects in hexagonal boron nitride (h-BN) play important roles in tunneling transport through the h-BN barrier. Here, using carbon-doped h-BN (h-BN:C) as a tunnel barrier containing defects in a controlled manner, we investigated tunneling transport through defects in the h-BN:C/graphene heterostructures. Defect-assisted tunneling through a specific kind of carbon-related defect was observed in all measured devices, where the defect level was always located at ∼0.1 eV above the graphene's charge neutrality point. We revealed a phonon-assisted inelastic process in the defect-assisted tunneling, in which carriers tunnel through the defect with phonon emission. Furthermore, when the h-BN:C barrier was thick (12 layers, ∼4 nm), sequential tunneling through two defects became dominant, where the phonon-assisted inelastic process shows substantial effects between the two defects. This study reveals the contribution of phonons to defect-assisted tunneling transport, which is essential for the development of defect-related van der Waals (vdW) electronic techniques.

Multi-species optically addressable spin defects in a van der Waals material

Optically addressable spin defects hosted in two-dimensional van der Waals materials represent a new frontier for quantum technologies, promising to lead to a new class of ultrathin quantum sensors and simulators. Recently, hexagonal boron nitride (hBN) has been shown to host several types of optically addressable spin defects, thus offering a unique opportunity to simultaneously address and utilise various spin species in a single material. Here we demonstrate an interplay between two separate spin species within a single hBN crystal, namely S = 1 boron vacancy defects and carbon-related electron spins. We reveal the S = 1/2 character of the carbon-related defect and further demonstrate room temperature coherent control and optical readout of both S = 1 and S = 1/2 spin species. By tuning the two spin ensembles into resonance with each other, we observe cross-relaxation indicating strong inter-species dipolar coupling. We then demonstrate magnetic imaging using the S = 1/2 defects and leverage their lack of intrinsic quantization axis to probe the magnetic anisotropy of a test sample. Our results establish hBN as a versatile platform for quantum technologies in a van der Waals host at room temperature.

Manipulating carbon related spin defects in boron nitride by changing the MOCVD growth temperature

A common solution for precise magnetic field sensing is to employ spin-active defects in semiconductors, with the NV center in diamond as a prominent example. However, the three-dimensional nature of diamond limits the obtainable proximity of the defect to the sample. Two-dimensional boron nitride, which can host spin-active defects, can be used to overcome those limitations. In this work, we study spin properties of sp2-bonded boron nitride layers grown using Metal Organic Chemical Vapor Deposition at temperatures ranging from 700 °C to 1200 °C. With Electron Spin Resonance (ESR) we show that our layers exhibit spin properties, which we ascribe to carbon related defects. Supported by photoluminescence and Fourier-transform infrared spectroscopy, we distinguish three different regimes: (i) growth at low temperatures with no ESR signal, (ii) growth at intermediate temperatures with a strong ESR signal and a large number of spin defects, (iii) growth at high temperatures with a weaker ESR signal and a lower number of spin defects. The observed effects can be further enhanced by an additional annealing step. Our studies demonstrate wafer-scale boron nitride that intrinsically hosts spin defects without any ion or neutron irradiation, which may be employed in spin memories or magnetic field detectors.

A quantum coherent spin in hexagonal boron nitride at ambient conditions.

Solid-state spin-photon interfaces that combine single-photon generation and long-lived spin coherence with scalable device integration-ideally under ambient conditions-hold great promise for the implementation of quantum networks and sensors. Despite rapid progress reported across several candidate systems, those possessing quantum coherent single spins at room temperature remain extremely rare. Here we report quantum coherent control under ambient conditions of a single-photon-emitting defect spin in a layered van der Waals material, namely, hexagonal boron nitride. We identify that the carbon-related defect has a spin-triplet electronic ground-state manifold. We demonstrate that the spin coherence is predominantly governed by coupling to only a few proximal nuclei and is prolonged by decoupling protocols. Our results serve to introduce a new platform to realize a room-temperature spin qubit coupled to a multiqubit quantum register or quantum sensor with nanoscale sample proximity.

Identifying the charge states of carbon vacancies in 4H-SiC by ab initio metadynamics

4H Silicon carbide (4H-SiC) is widely recognized as a highly promising material for high-voltage and high-power electronic applications due to its exceptional properties. The performance of devices based on 4H-SiC is often weakened by the presence of carbon-related point defects, particularly carbon vacancies (VC). The defects of VC introduce deep-level traps (e.g., Z1/2 and EH6/7) that deteriorate device functionality. Experimental and theoretical studies on VC have led to some conflicting results about the charge states of VC, especially for the charge state ordering of EH6/7. We now employ ab initio metadynamics (META) to systematically investigate configuration space including the direction and magnitude of bond distortion and identify the most stable structures of VC. Eventually, the charge states of VC in 4H-SiC are identified. The Z1 (EH6) and Z2 (EH7) indicate transitions from acceptor (donor) levels of VC, located on the h and k sublattice sites, respectively. Z1 and Z2 demonstrate negative-U ordering, characterized by U values of −0.16 and −0.37 eV, respectively. Conversely, EH6 and EH7 display positive-U ordering, with U values of 0.16 and 0.08 eV, respectively. The current results provide insights into the properties of VC in 4H-SiC, highlighting the effectiveness of META in the exploration of complex potential energy surfaces associated with point defects in solids.

Impact of carbon injection in 4H-SiC on defect formation and minority carrier lifetime

Point defects in silicon carbide (SiC) can act as charge carrier traps and have a pronounced impact on material properties such as the mobility and carrier lifetime. Prominent among these traps is the carbon vacancy (VC) with a demonstrated detrimental effect on the minority carrier lifetime in 4H-SiC epitaxial layers. Hence, a variety of methods for VC removal have been proposed. Common to all is that they involve some sort of C-injection into the epi-layer that leads to annihilation of VC with C interstitials (Ci) via the reaction Ci＋ VC→0̸. However, many studies on injection of Ci for removal of VC do not take into account the potential effect of any additional defects that are formed as a result of excess C in the material, including electrically active defects that introduce energy levels in the SiC band gap. Herein, we study the formation and impact of carbon related defects that are introduced in 4H-SiC epi-layers by injection of excess carbon. C-injection is achieved by annealing 4H-SiC epi-layers covered by a graphitized photoresist known as a C-cap at 1250°C for different durations. The resulting appearance of defects in the samples is monitored using deep level transient spectroscopy (DLTS) and minority carrier transient spectroscopy (MCTS) measurements, which reveal the formation of both minority and majority carrier traps as a result of the C-injection. Intriguingly, the injected carbon is also found to interact with a perennially present impurity in 4H-SiC epi-layers and a potentially lifetime limiting defect, namely boron. Furthermore, we monitor the minority carrier lifetime as a function of C-injection time and depth from the surface using cross-sectional time-resolved photoluminescence (TRPL) measurements. Both the defect distributions and the minority carrier lifetime are found to depend strongly on the duration of the C-cap anneal, with a marked depth dependence being present for all samples studied. The moderate temperature C-cap annealing treatment is proposed as a method for enhancing the carrier lifetime in n-type 4H-SiC epi-layers for power device applications.

Investigation of Current Collapse Mechanism on AlGaN/GaN Power Diodes

In this paper, a methodology is proposed for studying the current collapse effects of Gallium Nitride (GaN) power diodes and the consequences on the dynamic on-resistance (RON). Indeed, the growing interest of GaN based, high frequency power conversion requires an accurate characterization and a deep understanding of the device’s behaviour before any development of power converters. This study can ultimately be used to model observed trap effects and, thus, improve the equivalent electrical model. Using an in-house circuit and a specific experimental setup, a current-collapse phenomenon inherent to gallium nitride semiconductor is studied on planar 650 V—6 A GaN diodes by applying high voltage stresses over a wide range of temperatures. With this method, useful data on activation energy and capture cross section of electrical defects linked to dynamic RON are extracted. Finally, the origins of such defects are discussed and attributed to carbon-related defects.

Growth temperature induced changes of luminescence in epitaxial BN: from colour centres to donor-acceptor recombination.

Defects play a very important role in semiconductors and only the control over the defect properties allows the implementation of materials in dedicated applications. We present an investigation of the UV luminescence of defects in hexagonal boron nitride (h-BN) grown by Metal Organic Vapor Phase Epitaxy (MOVPE). Such intentionally introduced defects are important for applications like deep UV emission and quantum information. In this work, we performed photoluminescence and cathodoluminescence experiments on a set of h-BN layers grown by MOVPE at different growth temperatures (tgr). The obtained defect-related spectra in the ultraviolet range include well-known lines at about 230 nm (X230, hν = 5.4 eV) and 300 nm (C300 - the brightest one, hν = 4.14 eV) as well as a rarely observed band with a zero-phonon line at 380 nm (C380, hν = 3.24 eV). The C300 and C380 bands have the characteristic of a color centre showing sharp lines (0.6 nm width) at 5 K. These lines are most probably an internal transition of carbon-related defects. We show that for samples grown at high temperatures (tgr > 1200 °C), the lines related to the color centres C are replaced by broad bands at 330 nm and 400 nm, which we marked as D330 and D400, respectively. The D bands have similar central energies to the C bands but extend over a large energy range, so we propose that the D emission is due to a shallow donor to deep acceptor recombination. Time-resolved photoluminescence analysis determined the lifetimes of the individual lines in the range from 0.9 ns (C300), 1.8 ns (C380) to 4 ns (D400). The C300 and C380 color centre bands are composed of a series of characteristic lines that are due to the interaction with phonons. The E1u (198 meV) and A2u (93 meV) phonon replicas have been identified.

Hydroxyl-induced stability and mobility enhancement for field effect transistor based on In2O3 nanofiber

In this work, In2O3 nanofibers were fabricated by electrospinning, and a field effect transistor (FET) based on In2O3 nanofibers was integrated. A hydroxyl-assisted strategy was proposed for both stability and performance enhancement for the FET. Hydrogen peroxide (H2O2) was added into a precursor solution for electrospinning. It is found that the stability of the FET is improved after H2O2 incorporation, while the mobility is decreased. Surprisingly, after UV irradiation, the FET with both high mobility and high stability was obtained. It is assumed that under UV irradiation, H2O2 is decomposed into highly reactive hydroxyl radicals (•OH), which contributes to the degradation of the polymer. XPS and FT-IR analysis verify that oxygen- and carbon-related defects can be removed through the hydroxyl-assistant strategy. Furthermore, the flexible FET based on In2O3 nanofibers with H2O2 addition and UV irradiation was fabricated on the PI substrate, and the high electrical performance is further demonstrated. This strategy makes it possible to fabricate the oxide nanofiber FET with both high mobility and high stability.

Effect of Thermal Treatment of Symmetric TiO2 Nanotube Arrays in Argon on Photocatalytic CO2 Conversion

Symmetric titania nanotube arrays (TiO2 NTs) are a well-known photocatalyst with a large surface area and band edge potentials suitable for redox reactions. Thermal treatment of symmetrical arrays of TiO2 nanotubes in argon was used to change the carbon content of the samples. The influence of the carbon content in the structure of symmetrical TiO2 NTs on their photoelectrochemical properties and photocatalytic activity in the conversion of CO2 into organic fuel precursors has been studied. The structure, chemical, and phase composition of obtained samples were studied by X-ray analysis, Raman spectroscopy, and SEM with energy dispersive analysis. It is established that carbon-related defects in the samples accumulate electrons on the surface required for the CO2 conversion reaction. It has been shown for the first time that varying the carbon content in symmetric TiO2 NTs arrays by annealing at different temperatures in argon makes it possible to control the yield of methane and methanol in CO2 conversion. It is revealed that too high a concentration of carbon dangling bonds promotes the growth of CO2 conversion efficiency but causes instability in this process. The obtained results show a high promise of symmetric carbon-doped TiO2 NTs arrays for the photocatalytic conversion of CO2.

Computational prediction of stable semiconducting Zn-C binary compounds

Elemental carbon has been successfully used to tune the light emission properties of zinc oxide (ZnO) through artificially doping but the underlying mechanism remains controversial. At present, carbon-related defect complexes are the main explanation. Nevertheless, the possibility of forming semiconducting Zn-C compounds has not been discussed. In this study, we reveal the existence of various stable semiconducting Zn-C compounds. Based on particle swarm optimization and first-principles calculations, we perform a structural search of Zn-C binary compounds and report four stable semiconducting structures, in which the covalent Zn-C bonding characteristics are stronger compared with that in the metal rocksalt zinc carbide (ZnC). Crucially, three of the four Zn-C compounds have direct or quasi-direct band gaps in the range of 1.09–2.94 eV which are energies highly desirable for optoelectronic applications. Electronic transitions across the band gaps of these Zn-C structures could contribute to blue and near-infrared light emissions of C-doped ZnO. Our results have not only unraveled a new perspective to explain and tailor the light emission properties of ZnO but also provide a deeper understanding of possible Zn-C compounds.

Bistable carbon-vacancy defects in h-BN

Single-photon emitters in hexagonal boron nitride have been extensively studied recently. Although unambiguous identification of the emitters is still under intense research, carbon-related defects are believed to play a vital role for the emitter producing zero-phonon lines in the range of 1.6–2.2 eV. In this study, we systematically investigate two configurations of carbon-vacancy defects, VNCB and CNVB, by means of density functional theory calculations. We calculated the reaction barrier energies from one defect to the other to determine relative stability. We find that the barrier energies are charge dependent, and CNVB could easily transform to VNCB in neutral- and positive-charge states while it is stable when negatively charged. Formation energy calculations show that the VNCB is the dominant defect over CNVB. However, neither VNCB nor CNVB has suitable fluorescence spectra that could reproduce the observed ones. Our results indicate that the origin of the 1.6-to-2.2-eV emitters should be other carbon-related configurations.

Transient behavior of AlGaN photoluminescence induced by carbon-related defect reactions.

We have observed the transient behavior in the AlGaN photoluminescence. Under an excitation of 325 nm He-Cd laser beam, the blue luminescence (BL) bands and yellow luminescence (YL) bands of AlGaN vary with increasing illumination time. We propose that the chemical reactions between BL-related CNON-Hi (CN-Hi) and YL-related CN-Hi (CN) defect states are the cause of such a phenomenon. The BL transition temperature (Tt) is defined as the temperature at which the intensity of BL bands induced by CNON-Hi is equal to that originated from CN-Hi. Only at Tt, BL shows a peak energy variation due to the exposure. The Tt of AlGaN is higher than what is similarly detected in GaN because of the high reactivity of Al to O.

Comparative Study of Oxygen- and Carbon-Related Defects in Electron Irradiated Cz–Si Doped with Isovalent Impurities

Crystalline silicon (Si) is the key material of the semiconductor industry, with significant applications for electronic and microelectronic devices. The properties of Si are affected by impurities and defects introduced into the material either during growth and/or material processing. Oxygen (O) and carbon (C) are the main impurities incorporated into the crystal lattice during growth via the Czochralski method. Both impurities are electrically neutral, however, implantations/irradiations of Si lead to the formation of a variety of oxygen-related and carbon-related defects which introduce deep levels in the forbidden gap, inducing generally detrimental effects. Therefore, to control Si behavior for certain applications, it is important to have an understanding of the properties and fundamental processes related with the presence of these defects. To improve Si, isovalent doping during growth must be employed. Isovalent doping is an important defect-engineering strategy, particularly for radiation defects in Si. In the present review, we mainly focus on the impact of isovalent doping on the properties and behavior of oxygen-related and carbon-related defects in electron-irradiated Si. Recent experimental results from infrared spectroscopy (IR) measurements coupled with theoretical studies involving density functional theory (DFT) calculations, are discussed. Conclusions are reached regarding the role of isovalent doping (carbon, (C), germanium (Ge), tin (Sn), and lead (Pb)) on the suppression of detrimental effects introduced into Si from technologically harmful radiation clusters induced in the course of material processing.

Carbon-related defect control of bulk hBN single crystals growth by atmospheric-pressure metal-flux-based fusion synthesis

Carbon-related defect control of bulk hBN single crystals growth by atmospheric-pressure metal-flux-based fusion synthesis

Charge Trapping Mechanisms in Nitridated SiO<sub>2</sub>/ 4H-SiC MOSFET Interfaces: Threshold Voltage Instability and Interface Chemistry

Silicon dioxide (SiO2) layers deposited on 4H-SiC and subjected to different post deposition annealing (PDA) in NO and N2O were studied to identify the key factors influencing the channel mobility and threshold voltage stability in lateral implanted 4H-SiC MOSFETs. Cyclic gate bias stress measurements allowed to separate the contributions of interface states (Nit) and near interface oxide traps (NIOTs) in the two oxides. The reduction of these traps in the NO annealed sample is due to the lower amounts of sub-stoichiometric silicon oxide (~1nm) and carbon-related defects (<1nm) at the interface, as could be demonstrated by Electron Energy Loss Spectroscopy. The experimental results indicate that limiting the SiC re-oxidation during post-deposition annealing in MOSFET technology is a key factor to improve the mobility and threshold voltage stability.

Room-temperature optically detected magnetic resonance of single defects in hexagonal boron nitride

Optically addressable solid-state spins are important platforms for quantum technologies, such as repeaters and sensors. Spins in two-dimensional materials offer an advantage, as the reduced dimensionality enables feasible on-chip integration into devices. Here, we report room-temperature optically detected magnetic resonance (ODMR) from single carbon-related defects in hexagonal boron nitride with up to 100 times stronger contrast than the ensemble average. We identify two distinct bunching timescales in the second-order intensity-correlation measurements for ODMR-active defects, but only one for those without an ODMR response. We also observe either positive or negative ODMR signal for each defect. Based on kinematic models, we relate this bipolarity to highly tuneable internal optical rates. Finally, we resolve an ODMR fine structure in the form of an angle-dependent doublet resonance, indicative of weak but finite zero-field splitting. Our results offer a promising route towards realising a room-temperature spin-photon quantum interface in hexagonal boron nitride.

The structural and electronic properties of Carbon-related point defects on 4H-SiC (0001) surface

Carbon-related point defects on the 4H-SiC surface are essential for understanding the origin of defects at the SiO2/SiC interface and improving the quality of epitaxial materials. In this work, a first principle calculation was carried out to study the structural and electronic properties of carbon antisite (CSi), vacancy (VC) and interstitial defects (Ci1, Ci2, Ci3 and Ci4) on the 4H-SiC (0001) surface. The optimized structures showed that interstitial defects except Ci2 caused the surface reconstruction of 4H-SiC. The variation in formation energies with chemical potentials of the carbon for all defects indicated that the C-rich condition was beneficial to the formation of CSi, Ci1, Ci3 and Ci4, whereas the Si-rich condition was more favorable to VC. We also observed that these defects except Ci4 generated the corresponding defect energy levels in the bandgap of 4H-SiC by calculating the density of states and local charge densities. Furthermore, the effects of defect coverage and lateral lattice strain on structural and electronic properties of these defects were provided.

Rational Control on Quantum Emitter Formation in Carbon-Doped Monolayer Hexagonal Boron Nitride.

Single-photon emitters (SPEs) in hexagonal boron nitride (hBN) are promising candidates for quantum light generation. Despite this, techniques to control the formation of hBN SPEs down to the monolayer limit are yet to be demonstrated. Recent experimental and theoretical investigations have suggested that the visible wavelength single-photon emitters in hBN originate from carbon-related defects. Here, we demonstrate a simple strategy for controlling SPE creation during the chemical vapor deposition growth of monolayer hBN via regulating surface carbon concentration. By increasing the surface carbon concentration during hBN growth, we observe increases in carbon doping levels by 2.4-fold for B-C bonds and 1.6-fold for N-C bonds. For the same samples, we observe an increase in the SPE density from 0.13 to 0.30 emitters/μm2. Our simple method enables the reliable creation of hBN SPEs in monolayer samples for the first time, opening the door to advanced two-dimensional (2D) quantum state engineering.

Cathodoluminescence of carbon-related defects in hexagonal boron nitride

Hexagonal boron nitride is a wide band gap semiconductor exhibiting various luminescence bands in visible and near ultraviolet range, which can be used as single photon source. The luminescence band with zero phonon line at 4.1 eV is commonly ascribed to the carbon impurity introduced during crystal growth. In this paper we provide experimental evidence that carbon-related luminescent centers can be introduced in hBN by local electron irradiation in the chamber of scanning electron microscope at room temperature that can be used as a technique for the nanofabrication of single photon source devices with desired pattern.