Deep Level Centers Research Articles

Copper-rich complexes in irradiated silicon

Only copper-related deep-level centers are produced by room-temperature MeV-electron irradiation in silicon doped with a high concentration of mobile interstitial copper atoms. In oxygen-lean FZ-Si, the well-known CuPL centers of four copper atoms show up in the DLTS, Laplace-DLTS, and photoluminescence measurements. In oxygen-rich Cz-Si, two new centers appear due to the irradiation at the expense of the CuPL defect. Reaction kinetics analysis correlates the new defects with oxygen, copper, and the irradiation-induced vacancy. The new defects are annealed at temperatures of 150–250 °C and, after passing through two more new configurations, are transformed into CuPL. The strong similarities to CuPL suggest that all four new defects are CuPL-like complexes of four copper atoms perturbed by a nearby oxygen.

Carbon-related donor–acceptor pair transition in the infrared in h-BN

Experimental studies of intentionally doped impurities for the understanding of conductivity control in hexagonal boron nitride (h-BN) ultrawide bandgap (UWBG) semiconductor are limited but are highly desired for emerging applications of h-BN. We report synthesis by hydride vapor phase epitaxy and comparison photoluminescence (PL) emission spectroscopy studies of intentionally carbon (C)-doped and undoped h-BN semi-bulk crystals. In addition to the well-known C-related emission lines observed previously, a C-impurity-related transition near 1.31 eV consisting of multiple phonon replicas has been observed in C-doped h-BN at room temperature. Phonon replicas involved in the 1.31 eV emission have been identified using polarization resolve PL spectroscopy as the transverse acoustic (TA)/longitudinal acoustic (LA) and out-of-plane optical phonon (ZO) modes at the middle point, T, between the Γ- and K-points in the first Brillouin zone. Based on the agreement between the spectral peak position of the observed dominant emission line at 1.31 eV and the calculated energy-level separation between CB donor (carbon replacing boron) and Ci acceptor (carbon interstitial), the observed IR emission line can be decisively assigned to the donor–acceptor pair (DAP) transition involving the CB donor and Ci acceptor assisted by the intervalley (Κ → Μ) scattering processes. The results reinforce the perception that C impurities form deep-level centers and provided an improved understanding of C impurities in h-BN.

The application of the SCAN density functional to color centers in diamond.

Detailed characterization of deep-level color centers requires understanding their electronic and atomic structure, which is most commonly investigated utilizing the Kohn-Sham density functional theory. Standard semilocal functionals based on the generalized gradient approximation (GGA) are inclined toward an imprecise quantitative description of defects' electronic structure. Hybrid functionals provide an improved prediction of electronic properties, albeit at a much higher computational cost. In this work, we test the newly developed Strongly Constrained and Appropriately Normed (SCAN) family of meta-GGA density functionals for selected color centers in diamond. In particular, we study nitrogen-, silicon-, germanium-, and tin-vacancy centers that have been recently investigated for their use in quantum technological applications. We show that SCAN and its derivatives, the rSCAN and r2SCAN functionals, significantly improve the calculated energies of optical transitions within the delta-self-consistent-field approach, almost reaching the accuracy of the hybrid Heyd-Scuseria-Ernzerhof (HSE) functional. In the case of the NV- center, we also show that the SCAN family of functionals improves the description of the adiabatic potential energy surfaces compared to both GGA and hybrid functionals, improving calculated luminescence lineshapes. As a result of these findings, we recommend using the SCAN family of functionals as a promising alternative for studying color centers in solids.

Intrinsic defects in B-site columnar-ordered halide double perovskites Cs2AgPdBr5.

Cs2AgPdBr5 is a new type of double perovskite with one-dimensional electronic dimensionality, which is expected to be a promising candidate of photovoltaic materials. Considering that defects usually exist in real materials, in this study, we investigate the intrinsic defect properties of Cs2AgPdBr5 from first principles. First, the phase diagram of Cs2AgPdBr5 is calculated. It turns out that its thermodynamic stable region is small, suggesting that the growth conditions should be carefully controlled to obtain high-quality samples. By systematically investigating the Fermi-level pinning behavior, we find that p-type Cs2AgPdBr5 can be obtained at an Ag-poor condition. At the same time, Pd2+i and Pd1+Ag are the only two deep-level recombination centers at 300 K. Therefore, if possible, the amount of palladium should be relatively small in the synthesis process. Our study provides guidance to obtain high-performance Cs2AgPdBr5 materials for photovoltaic applications.

Synthesis and Characterization of Nanoporous ZnO Films by Controlling the Zn Sublimation by Using ZnO/Zn Precursor Films.

A reliable process for the formation of nanoporous ZnO films supported on amorphous quartz and (100) silicon substrates via the processing of ZnO/Zn precursor films is reported. The process is based on the sublimation mechanism of Zn implemented in a novel ZnO/Zn precursor film to produce a nanoporous film. A scanning electron microscopy analysis of the nanoporous ZnO films’ surfaces revealed the presence of ZnO nano-features with round tips; in contrast, the nanoporous ZnO films supported on (100) Si substrates showed hexagonal nut-like nanostructures. The crystallite size of the nanoporous ZnO films decreased as the sublimation temperature was increased. X-ray photoelectron spectroscopy studies demonstrated that formations of oxygen vacancies were produced during the processing stages (as the main structural lattice defects in the ZnO nanoporous films). The analysis of the photoluminescence response confirmed that the active deep-level centers were also related to the oxygen vacancies generated during the thermal processing of the ZnO/Zn precursor films. Finally, a qualitative mechanism is proposed to explain the formation of nanoporous ZnO films on quartz and crystalline Si substrates. The results suggest that the substrates used have a strong influence on the nanoporous ZnO structures obtained with the Zn-sublimation-controlled process.

Локализация носителей заряда в квантовых ямах InGaN/GaN, ограниченная объемным зарядом

The mechanism of carrier tunneling through the potential walls of InGaN/GaN quantum well in the p-n structures is studied by means of the deep center tunneling spectroscopy. A number of humps on the current and photocurrent tunneling spectra, as well as on the forward bias dependences of the intensity and the peak energy of photoluminescence band from the quantum well are detected. These findings allow us to propose a model of carrier localization in the quantum well that permit to relate the tunneling transparency of the potential walls of the QW to the space-charge of deep-level centers in the quantum well barriers and its changes under optical excitation and forward biasing of p-n structure.

Space-charge-limited carrier localization in InGaN/GaN quantum wells

The mechanism of carrier tunneling through the potential walls of InGaN/GaN quantum well in the p-n-structures is studied by means of the deep center tunneling spectroscopy. A number of humps on the current and photocurrent tunneling spectra, as well as on the forward bias dependences of the intensity and the peak energy of photoluminescence band from the quantum well are detected. These findings allow us to propose a model of carrier localization in the quantum well that permit to relate the tunneling transparency of the potential walls of the QW to the space-charge of deep-level centers in the quantum well barriers and its changes under optical excitation and forward biasing of p-n-structure. Keywords: gallium nitride, quantum well, photoluminescence, deep center tunneling spectroscopy, impurity color centers.

Short wavelength infrared (SWIR) spectroscopy of phyllosilicate minerals from the Tonglushan Cu-Au-Fe deposit, Eastern China: New exploration indicators for concealed skarn orebodies

The Middle–Lower Yangtze River Metallogenic Belt (MLYRB) is one of the most important Cu–Au–Fe–Mo skarn–porphyry metallogenic belts in Eastern China. After several decades of mining, the shallow-level mineral resources have been gradually exhausted, which call for new exploration tools for concealed orebodies. The Tonglushan Cu–Au–Fe skarn deposit (86.3 Mt @ 1.66% Cu, 0.94 g/t Au and 39.4% Fe) is located in the western MLYRB. Skarn alteration/mineralization are mainly hosted in the contact zone between Cretaceous (~141 Ma) quartz monzodiorite (and its porphyry) and the Lower Triassic carbonate rocks. Based on the mineral assemblages and their macro/microscopic textural relationships, the Tonglushan Cu–Au–Fe mineralization/alteration can be divided into five stages: pre-ore (S1: skarn–potassic alteration), Fe ore (S2: retrograde alteration and Fe-oxides), Cu–Au ore (S3: quartz–sulfides), carbonate alteration (S4) and supergene alteration (S5). Apart from the major skarn and retrograde alteration and carbonate minerals, abundant fine-grained phyllosilicate minerals, including chlorite, white mica (illite, muscovite and phengite), smectite (montmorillonite and saponite) and kandite (kaolinite, dickite and halloysite) group minerals have been identified at Tonglushan by SWIR spectrometry. Integrating petrographic observations and SWIR spectral analysis, four alteration zones (with distinct phyllosilicate assemblages) have been distinguished from the intrusion outward: (I) ore-barren quartz monzodiorite and its porphyry (montmorillonite–illite–chlorite), (II) endoskarn close to the skarn–hydrothermal mineralization center (montmorillonite–illite–chlorite–kaolinite–dickite), (III) skarn–hydrothermal mineralization center (saponite–chlorite), and (IV) the external contact zone in (dolomitic) marble (montmorillonite–chlorite ± kaolinite ± dickite).For the Tonglushan altered rock samples, SWIR spectrometry has identified wavelength shifts in the Fe–OH, Al–OH and sub-Al–OH absorption features of chlorite, white mica–montmorillonite and kandite, respectively. Chlorite Fe–OH absorption occurs at longer wavelengths (>2,250 nm), white mica–montmorillonite Al–OH absorption occurs at unusually long (>2,212 nm) and short (<2,202 nm) wavelengths, and kandite sub-Al–OH absorption occurs at longer wavelengths (>2,170 nm) in strongly-altered skarn proximal samples. Moreover, the presence of kaolinite, dickite, saponite, actinolite, phlogopite and/or chlorite–quartz–sulfides veins in these samples can be used as new vectors to explore deep-level mineralization centers at Tonglushan. The distribution of various kinds of phyllosilicate alteration minerals at Tonglushan, especially the white mica and kandites (with higher crystallinity) in the deep contact zones, indicates that the neutral to acidic hydrothermal fluids may have been generated with the precipitation of Fe-oxides and sulfides. This study also highlights the potential of SWIR spectroscopy of phyllosilicate minerals for exploring concealed skarn orebodies in the MLYRB.

Apparatus for electrically detected electron nuclear double resonance in solid state electronic devices.

We have developed a sensitive electron nuclear double resonance spectrometer in which the detection takes place through electrically detected magnetic resonance. We demonstrate that the spectrometer can provide reasonably high signal to noise spectra of 14N interactions with deep level centers in a fully processed bipolar junction transistor at room temperature.

On the Characteristic Features of the Impurity Energy Spectrum in Arsenides

The impurity energy spectrum of undoped n-type GaAs, InAs, CdSnAs2, CdGeAs2, and CdTe, ZnO bulk crystals is studied based on a quantitative analysis of the baric and temperature dependences of the kinetic coefficients. It is found that the deep-level donor center corresponds to the intrinsic vacancy defect in the anion sublattice in the above-listed semiconductors. The conclusion on the nature of the donor center, i.e., the vacancy in the anion sublattice, is based on the fact that, in contrast to shallow impurity centers which trace the intrinsic band under uniform pressure, to which they are genetically related, the energy of deep impurity centers with respect to absolute vacuum remains constant under isotropic compression of the lattice. Therefore, it seems favorable to study the evolution of the carrier energy spectrum in semiconductors under uniform-pressure conditions. The energy-level positions with respect to the conduction-band edge and pressure coefficients of the energy gaps between them and the corresponding conduction-band bottom are determined. The shift of the energy level of the deep donor center to the conduction-band depth with decreasing band gap is observed.

Interplay of carriers and deep-level recombination centers of 275-nm light-emitting diodes - Analysis on the parasitic peaks over wide ranges of temperature and injection density.

The low luminance efficiency, poor reliability and parasitic peaks have greatly limited the commercialization of deep ultraviolet (DUV) light-emitting diodes. Tasks of identifying the culprits of these deficits are of paramount importance but remains unaccomplished. We employ the full-range temperature (20 K -300 K) measurement on 275-nm DUV devices that subjected to a 15-hour current-stress aging. The results suggest that the primary culprit of fast luminous decay is the proliferation of non-radiative centers. The origins of two main parasitic peaks are identified. The 310-nm peak is considered to solely come from deep-level radiative centers (DLRCs) that only dwell in the active region. Whereas, the 400-nm peak is proven to be dual-sources. One is related to the DLRCs in the active region, which only can be observed at very low currents; the other emerging at higher currents are associated with similar kinds of DLRCs located in the p-region, which only are excited when electrons overflow. This new discovery also demonstrates that a thorough investigation on the interplay among carriers and various types of defects should be conducted on the basis of the measurement that is taken under a wide temperature range, as well as under a proper forward voltage. This is to let the quasi-Fermi level shift across deep defect levels, the band-edge, and to over-band, whereby these recombination sites are exposed to deficit, moderate and saturated electron environment so that their natures can be well tested.

Photoconductive terahertz detectors with 105 dB peak dynamic range made of rhodium doped InGaAs

Rhodium (Rh)-doped In0.53Ga0.47As grown by gas-source molecular beam epitaxy is investigated as a terahertz (THz) detector antenna for optical excitation at 1550 nm. The 4d transition metal rhodium acts as a deep level and ultrafast trapping center. At a doping concentration around 8 × 1019 cm−3, InGaAs:Rh exhibits ideal properties for application as a THz antenna: an ultrashort carrier lifetime below 200 fs in combination with a mobility of 1010 cm2/Vs. The THz detectors fabricated from this sample show a record peak dynamic range of 105 dB and a bandwidth of up to 6.5 THz.

Role of interstitial hydrogen in SrCoO2.5 antiferromagnetic insulator

Hydrogen exhibits qualitatively different charge states depending on the host material, as nicely explained by the state-of-the-art impurity-state calculation. Motivated by a recent experiment [Nature 546, 124 (2017)], we show that the complex oxide SrCoO$_{2.5}$ represents an interesting example, in which the interstitial H appears as a deep-level center according to the commonly-used transition level calculation, but no bound electron can be found around the impurity. Via a combination of charge difference analysis, density of states projection and constraint magnetization calculation, it turns out that the H-doped electron is spontaneously trapped by a nonunique Co ion and is fully spin-polarized by the onsite Hund's rule coupling. Consequently, the doped system remains insulating, whereas the antiferromagnetic exchange is slightly perturbed locally.

Influence of dislocation density and carbon impurities in i-GaN layer on the performance of Schottky barrier ultraviolet photodetectors

The influences of dislocation density and carbon impurities in i-GaN layer on the performance of Schottky barrier ultraviolet photodetectors are investigated. It is found that an increase in dislocation density leads to a decrease in the responsivity, mainly because that the dislocation defects act as charge traps in GaN which can increase the recombination probability of photo-generated electron-hole pairs. On the other hand, it is shown that high carbon impurity content in the i-GaN layer also causes a decrease of the responsivity, mainly because the fact that the photo-generated carriers can’t be effectively collected due to the effect of C-induced deep level centers related to carbon impurities.To fabricate high performance GaN based ultraviolet photodetectors, it is important to reduce dislocation density and keep a relatively low concentration of residual carbon during the material growth.

FREE CARRIER RECOMBINATION LIFETIME CALCULATION FROM PHOTOCONDUCTIVITY DECAY MEASUREMENT IN NON–PASSIVATED SILICON

In indirect band gap semiconductors, for example, in silicon, the free carrier recombination lifetime is determined by recombination through deep level centers and inversely proportional to their concentration. This parameter is of the utmost importance for characterizing the quality of the material. Contactless methods of free carrier recombination lifetime measurements by protoconductivity decay analysis are most widely used. The measurement results are largely affected by surface recombination. The calculation of the lifetime in the bulk of a sample from the characteristic time of photoconductivity decay remains relevant since there is no ambiguous analytical solution of the continuity equation for this case. In this paper, an analysis of the relaxation of photoconductivity in single−crystal silicon wafers with non−passivated surfaces was carried out with numerical methods. The applicability of the well–known formulas for estimating the contribution of surface recombination to the effective photoconductivity decay time was discussed. We show that the time in which the «fast» exponents disappear depends on the relative thickness of the sample. It is only this part of the relaxation curve that the effective decay time is determined by the maximum value of the surface component of the relaxation time and is described by the well−known formulas. The saturation of the effective relaxation time at the point when the signal intensity reaches 45 % of the peak one (the onset point of effective decay time counting pursuant to the SEMI MF 1535 standard recommendation) only occurs in samples with thicknesses less than 3—5 diffusion lengths. For thick samples the contribution of the «fast» exponentials to the effective photoconductivity relaxation time is observed up to 5 % of the peak signal (i.e., until the noise level of the measured signal is reached). Use of the recommended formulas, including for the «infinite recombination rate» case at which the maximum surface lifetime is d2/π2D, leads to a sufficiently large (up to 20 %) error in free carrier recombination lifetime calculation.

First-principle calculation of electronic structures and absorption spectra of lithium niobate crystals doped with Co and Zn ions

In this paper, the electronic structures and absorption spectra of Co doped and Co, Zn co-doped LiNbO3 crystals are studied by the first-principle using the density functional theory, to explore the characteristics of charge transfer in Co, Zn co-doped LiNbO3 crystals, and to build the relationship between these characteristics and the holographic storage quality. The basic model is built as a supercell structure of 211 of near-stoichiometric pure LiNbO3 crystal with 60 atoms, including 12 Li atoms, 12 Nb atoms and 36 O atoms. Four models are established as the near-stoichiometric pure LiNbO3 crystal (LiNbO3), the cobalt doped LiNbO3 crystal (Co:LiNbO3), the zinc and cobalt co-doped LiNbO3 crystal [Co:Zn(L):LiNbO3] with doping ions at Li sites, and the other zinc and cobalt co-doped LiNbO3 crystal [Co:Zn (E):LiNbO3)] with zinc ions at Li sites and Nb sites. The last two models would represent the concentration of Zn ions below the threshold (6 mol%) and near the threshold, respectively. The charge compensation forms are taken as CoLi+-VLi-, CoLi+-ZnLi+-2VLi- and CoLi+-ZnNb3--2ZnLi+ respectively in doped models. The results show that the conduction band and valence band of pure LiNbO3 crystal are mainly composed of O 2p orbit and Nb 4d orbit respectively, and energy gap is 3.48 eV. The band gap of the doped LiNbO3 crystal is narrower than that of pure LiNbO3 crystal, due to the Co 3d and Zn 3d orbit energy levels superposed with that of O 2p orbit energy levels, and thus forming the upside of covalent bond. The band gap of Co:LiNbO3 crystal is 3.32 eV, and that of Co:Zn:LiNbO3 crystals are 2.87 eV and 2.75 eV respectively for Co:Zn(L):LiNbO3 and Co:Zn(E):LiNbO3 model. The Co 3d orbit is split into eg orbit and t2g orbit with different energies. The absorption peak at 2.40 eV appears in the band gap of Co:LiNbO3 crystal, which is attributed to the transfer of the Co 3d splitting orbital t2g electrons to conduction band. The absorption peaks of 1.58 eV and 1.10 eV could be taken as the result of eg electron transfers of both Co2+ and Co3+ in crystal, especially the latter ion. These two absorption peaks are obviously enhanced in Co:Zn (E):LiNbO3 crystal compared with in other samples in this paper. Based on that, it could be proposed that a charge transfer between Zn2+ and Co2+ as Co2++Zn2+Co3++Zn+ exist in the crystal, which results in the decrease of eg orbital electron number, but hardly affect the t2g orbital electron. The Co ion in crystal could act as the deep-level center (2.40 eV) or the shallow-level center (1.58 eV) with the different accompanying doped photorefractive ions in the two-light holographic storage applications. In both cases, the choice of Zn ion concentration near threshold could be helpful for the photo damage resistance and recording light absorption in storage applications.

The TRAMOS pixel as a photo-detection device: Design, architecture and building blocks

The deep trapping gate device concept for charged particle detection was recently introduced in Saclay/IRFU. It is based on an n-MOS structure in which a buried gate, located below the n-channel, collects carriers which are generated by ionizing particles. They deposit their energy in a volume which extends in the bulk, below the buried gate. The n-channel device is based on holes in-buried gate localization. Source–drain current modulation occurs, measurable during readout. The buried gate (Deep Trapping Gate or DTG) contains deep level centers which can be introduced during process or may be made with a Quantum Well. The device can be scaled down providing a micron range resolution. The proof of principle for such a device was verified using 2D device and process simulations. Work under way focusses on the study of building blocks. In this contribution, the pixel proof of design, using existing fabrication techniques will be discussed first. The use of this pixel for photon imaging will be discussed.

Capacitance spectroscopy on n-type GaNAs/GaAs embedded quantum structure solar cells

In this study, both deep level transient spectroscopy (DLTS) and admittance spectroscopy (AS) have been used to study the properties of electrically active deep level centers present in GaNAs/GaAs quantum wells (QWs) embedded in p-i-n solar cells. The structures were grown by molecular beam epitaxy (MBE). In particular, the electrical properties of samples with Si (n-type) doping of the QWs were investigated. DLTS revealed four deep level centers in the material, whereas only three were detected by AS. NextNano++ simulation software was used to model the sample band-diagrams to provide reasoning for the origin of the signals produced by both techniques.

Deep level centers in electron‐irradiated silicon crystals doped with copper at different temperatures

The effect of bombardment with energetic particles on the deep‐level spectrum of copper‐contaminated silicon wafers is studied by space charge spectroscopy methods. The p‐type FZ‐Si wafers were doped with copper in the temperature range of 645–750 °C and then irradiated with the 1015 cm−2 fluence of 5 MeV electrons at room temperature. Only the mobile Cui species and the CuPL centers are detected in significant concentrations in the non‐irradiated Cu‐doped wafers. The properties of the irradiated samples are found to qualitatively depend on the copper in‐diffusion temperature Tdiff. For Tdiff &gt; 700 °C, the irradiation partially reduces the Cui concentration and introduces additional CuPL centers while no standard radiation defects are detected. If Tdiff was below ∼700 °C, the irradiation totally removes the mobile Cui species. Instead, the standard radiation defects and their complexes with copper appear in the deep‐level spectrum. A model for the defects reaction scheme during the irradiation is derived and discussed.DLTS spectrum of the Cu‐contaminated and then irradiated silicon qualitatively depends on the copper in‐diffusion temperature.

Quasi-streamer mode of delayed avalanche breakdown initiated by technological imperfections

Numerical simulations of spatially non-uniform picosecond-range switching of high-voltage silicon diodes with technological imperfections have been performed. It is shown that spatially inhomogeneous distribution of process-induced deep-level centers that trigger ionization process easily provoke current localization. A fluctuation of concentration with a relative amplitude of 10% leads to almost complete localization of current. The switching time sharply decreases (from ∼100 ps to ∼10 ps) with the increase of the amplitude of the inhomogeneity and the decrease of its size.