Deep Acceptor Research Articles

Preparation and characterization of SbSeI thin films

Metal chalcohalides are promising candidates for next-generation technologies that include energy conversion, information storage, and quantum computing. Among them, antimony selenoiodide (SbSeI) has received rising interest for different optoelectronic devices, including photovoltaics, due to its bandgap energy, strong optical absorption, stability, and earth abundant, low-cost, and low toxicity constituents. In this work, SbSeI thin films were prepared through a two-step process. At first, antimony selenide (Sb2Se3) thin films were deposited at 300 °C (Sb2Se3-300) and at room temperature (Sb2Se3-RT) onto molybdenum covered soda-lime glass substrates by a magnetron sputtering method. The formation of SbSeI thin films was performed by isothermally annealing the as-deposited Sb2Se3 thin films in sealed quartz ampoules in the atmosphere of antimony iodide (SbI3) with the presence of 100 Torr of argon pressure. The influence of the annealing temperature and time during the iodization of different types of substrates on the morphology and composition of SbSeI thin films was investigated. The well-oriented and dense single-phase SbSeI thin films with stoichiometric composition and single-crystal micro-columnar structures were achieved by annealing Sb2Se3-RT in SbI3 atmosphere at 250 °C for 5 min under 100 Torr of Ar pressure. The room temperature photoluminescence (RT-PL) of SbSeI exhibited a broad asymmetric PL band with a maximum at 1.67 eV. The low-temperature (T = 8 K) PL study of SbSeI showed a broad and asymmetric PL band at 1.4 eV, being quite distant from the bandgap. This PL band at 1.4 eV with obtained small thermal quenching activation energy of 12.7 meV is proposed to originate from the deep donor-deep acceptor pair (DD-DA) recombination.

Direct Observation of the Stretching of the Photoinduced Current Relaxation in α-Ga2O3 Schottky Diodes

Relaxation of photoinduced current in α-Ga2O3-based Schottky diodes was measured. Such Schottky diodes were fabricated using α-Ga2O3 films grown by Halide Vapor Phase Epitaxy (HVPE) on basal plane sapphire. Their photosensitivity in UV-C region was very high and several orders of magnitude higher than for visible light. The photoinduced current rise and decay times are found to be quite long, which is attributed to the hole capture by deep acceptors and to the effects of potential fluctuations. Due to these problems the photoinduced current relaxation process consists of several steps and takes more than hundreds of seconds. The characteristic relaxation times were calculated using the logarithmic differential analysis that demonstrated that the build-up and decay processes can be accurately described by stretched exponents with different broadening factors β. It was shown that additional illumination by long-wave light can help to observe the slowing of the relaxation speed. The temperature activation energies for photoinduced current decay and rise times are 0.37 ± 0.03 eV and 0.06 ± 0.005 eV respectively.

Electrical properties of silicon-implanted β-Ga2O3:Fe crystals

Ion implantation is a promising method for the development of β-Ga2O3-based technologies and devices. However, the physical principles of ion implantation for this particular semiconductor are still at the early stage of development. One of the primary tasks is the study of electrical properties of the ion-doped layers. In this work, we have investigated the electrical parameters of layers produced by ion implantation of a shallow donor impurity—silicon—into a semi-insulating β-Ga2O3 doped with iron and having a surface orientation of (−201). It is established that the activation efficiency of the implanted impurity significantly exceeds unity after post-implantation annealing at high temperatures. This indicates that not only silicon itself contributes to conductivity, but also defects formed with its (and, probably, iron) participation are involved. The temperature dependence of electron mobility is consistent with the theoretically calculated one under the assumption that, apart from shallow donors, there are also deep defect-associated donors and acceptors. It is assumed that the established properties are specific for the case of direct Si implantation into β-Ga2O3 doped with Fe.

Identification and characterization of deep nitrogen acceptors in β-Ga2O3 using defect spectroscopies

The ability to achieve highly resistive beta-phase gallium oxide (β-Ga2O3) layers and substrates is critical for β-Ga2O3 high voltage and RF devices. To date, the most common approach involves doping with iron (Fe), which generates a moderately deep acceptor-like defect state located at EC-0.8 eV in the β-Ga2O3 bandgap. Recently, there has been growing interest in alternative acceptors, such as magnesium (Mg) and nitrogen (N), due to their predicted deeper energy levels, which could avoid inadvertent charge modulation during device operation. In this work, a systematic study that makes direct correlations between the introduction of N using ion implantation and the observation of a newly observed deep level at EC-2.9 eV detected by deep-level optical spectroscopy (DLOS) is presented. The concentration of this state displayed a monotonic dependence with N concentration over a range of implant conditions, as confirmed by secondary ion mass spectrometry (SIMS). With a near 1:1 match in absolute N and EC-2.9 eV trap concentrations from SIMS and DLOS, respectively, which also matched the measured removal of free electrons from capacitance-voltage studies, this indicates that N contributes a very efficiently incorporated compensating defect. Density functional theory calculations confirm the assignment of this state to be an N (0/−1) acceptor with a configuration of N occupying the oxygen site III [NO(III)]. The near ideal efficiency for this state to compensate free electrons and its location toward the midgap region of the β-Ga2O3 bandgap demonstrates the potential of N doping as a promising approach for producing semi-insulating β-Ga2O3.

Role of Native Defects in Fe-Doped β-Ga2O3.

Iron impurities are believed to act as deep acceptors that can compensate for the n-type conductivity in as-grown Ga2O3, but several scientific issues, such as the site occupation of the Fe heteroatom and the complexes of Fe-doped β-Ga2O3 with native defects, are still lacking. In this paper, based on first-principle density functional theory calculations with the generalized gradient approximation approach, the controversy regarding the preferential Fe incorporation on the Ga site in the β-Ga2O3 crystal has been addressed, and our result demonstrates that Fe dopant is energetically favored on the octahedrally coordinated Ga site. The structural stabilities are confirmed by the formation energy calculations, the phonon dispersion relationships, and the strain-dependent analyses. The thermodynamic transition level Fe3+/Fe2+ is located at 0.52 eV below the conduction band minimum, which is consistent with Ingebrigtsen's theoretical conclusion, but slightly smaller than some experimental values between 0.78 eV and 1.2 eV. In order to provide direct guidance for material synthesis and property design in Fe-doped β-Ga2O3, the defect formation energies, charge transitional levels, and optical properties of the defective complexes with different kinds of native defects are investigated. Our results show that VGa and Oi can be easily formed for the Fe-doped β-Ga2O3 crystals under O-rich conditions, where the +3 charge state FeGaGai and -2 charge state FeGaOi are energetically favorable when the Fermi level approaches the valence and conduction band edges, respectively. Optical absorption shows that the complexes of FeGaGai and FeGaVGa can significantly enhance the optical absorption in the visible-infrared region, while the energy-loss function in the β-Ga2O3 material is almost negligible after the extra introduction of various intrinsic defects.

Electrical characteristics of in situ Mg-doped β-Ga2O3 current-blocking layer for vertical devices

The lack of p-type doping has impeded the development of vertical gallium oxide (Ga2O3) devices. Current blocking layers (CBLs) using implanted deep acceptors have been used to demonstrate vertical devices. This paper presents a pioneering demonstration of in situ Mg-doped β-Ga2O3 CBLs grown using metal–organic chemical vapor deposition. The Mg-doping density during growth was calibrated by quantitative secondary ion mass spectroscopy. Electrical test structures were designed with in situ Mg doped layers with various targeted Mg doping concentrations. The effectiveness of the CBL is characterized by using temperature-dependent current–voltage measurements using n-Mg-doped-n structures, providing crucial insight into the underlying mechanisms. Pulsed measurements show similar blocking characteristics as DC. To further validate the experimental results, a TCAD simulation is performed, and the electrically active effective doping is found to be dependent on the Mg-doping density, offering an alternate perspective on the optimization of CBL performance. Breakdown measurements show a peak 4 MV/cm field strength.

Boosting the open-circuit voltage of Cu2ZnSn(S,Se)4 solar cell by Cd/NH3 soaking

In this paper, the open-circuit voltages (V OC) of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells were improved by soaking the CZTSSe films in Cd/NH3 solutions before the deposition of buffer layers. The effects of Cd/NH3 soaking on the properties of CZTSSe films and solar cells were investigated in depth. We found Cd/NH3 soaking can promote downward band bending of the CZTSSe layer at the surface region. In addition, the Cd/NH3 soaking can eliminate the deep level acceptor in CZTSSe and decrease the density of the defects at the absorber/buffer interface. These effects can significantly reduce the carrier recombination in the depletion region of CZTSSe solar cells. As a result, the V OC of CZTSSe solar cells were increased from ∼460 mV to ∼480 mV, the efficiency of the best CZTSSe solar cell was increased from 10.2% to 11.6% by the Cd/NH3 soaking process.

High-throughput and cost-effective method for production of high-quality semi-insulating InP substrates

A novel technique for preparation of high-resistivity indium phosphide (InP) via post-growth treatment of undoped n-type wafers is presented. The method includes the deposition of a controlled quantity of iron on both faces of as-cut wafers by a simple chemical bath, and the subsequent Fe diffusion by thermal annealing. The reproducible low - to – high resistivity conversion is explained considering two simultaneous phenomena: the annealing-controlled in-diffusion of Fe deep acceptors and the out-diffusion of hydrogen-related shallow donors. Differently from standard Fe-doped melt-grown InP single crystals, this process does not suffer from segregation, thus the Fe-concentration is constant from wafer to wafer, with no striations and radial gradients deriving from the convex solid–liquid interface during growth. Main advantages of the developed process are: i) an entire undoped InP boule may be sliced and converted to semi-insulating, which makes the process cost-effective; ii) reproducible and uniform semi-insulating properties from batch to batch of wafers; iii) the Fe incorporation is precisely controlled, and minimized, so that electrical characteristics of Fe-diffused wafers are superior to those of traditional semi-insulating melt-grown InP crystals doped via addition of elemental Fe to the melt.

Probing Boron Vacancy Complexes in h-BN Semi-Bulk Crystals Synthesized by Hydride Vapor Phase Epitaxy

Hexagonal BN (h-BN) has emerged as an important ultrawide bandgap (UWBG) semiconductor (Eg~6 eV). The crystal growth technologies for producing semi-bulk crystals/epilayers in large wafer sizes and understanding of defect properties lag decades behind conventional III-nitride wide bandgap (WBG) semiconductors. Here we report probing of boron vacancy (VB)-related defects in freestanding h-BN semi-bulk wafers synthesized by hydride vapor phase epitaxy (HVPE). A photocurrent excitation spectroscopy (PES) was designed to monitor the transport of photoexcited holes from deep-level acceptors. A dominant transition line at 1.66 eV with a side band near 1.62 eV has been directly observed, which matches well with the calculated energy levels of 1.65 for the VB-H deep acceptor in h-BN. The identification of VB complexes via PES measurement was further corroborated by the temperature-dependent dark resistivity and secondary ion mass spectrometry measurements. The results presented here suggested that it is necessary to focus on the optimization of V/III ratio during HVPE growth to minimize the generation of VB-related defects and to improve the overall material quality of h-BN semi-bulk crystals. The work also provided a better understanding of how VB complexes behave and affect the electronic and optical properties of h-BN.

Properties of κ‐Ga2O3 Prepared by Epitaxial Lateral Overgrowth

AbstractThe structural and electrical properties of undoped and Sn doped κ‐Ga2O3 layers grown by epitaxial lateral overgrowth on TiO2/sapphire substrates using stripe and point masks show that the crystalline structure of the films can be greatly improved relative to conventional planar growth. The undoped films are semi‐insulating, with the Fermi level pinned near EC‐0.7 eV, and deep electron traps at EC‐0.5 eV and EC‐0.3 eV are detectable in thermally stimulated current and photoinduced current transient spectra measurements. Low concentration Sn doping results in net donor concentrations of ≈ 1013 cm−3, and deep trap spectra determined by electron traps at EC‐0.5 eV, and deep acceptors with an optical ionization threshold near 2 and 3.1 eV. Treatment of the samples in hydrogen plasma at 330 °C increases the donor density near the surface to ≈ 1019 cm−3. Such samples show strong persistent photocapacitance and photoconductivity, indicating the possible DX‐like character of the centers involved. For thin (5 µm) κ‐Ga2O3 films grown on GaN/sapphire templates, p‐type‐like behavior is unexpectedly observed in electrical properties and we discuss the possible formation of a 2D hole gas at the κ‐Ga2O3/GaN interface.

Effect of induced defects on conduction mechanisms of noble-gas-implanted ScN thin films

Noble-gas implantation was used to introduce defects in n-type degenerate ScN thin films to tailor their transport properties. The electrical resistivity increased significantly with the damage levels created, while the electron mobility decreased regardless of the nature of the ion implanted and their doses. However, the transport property characterizations showed that two types of defects were formed during implantation, named point-like and complex-like defects depending on their temperature stability. The point-like defects changed the electrical conduction mode from metallic-like to semiconducting behavior. In the low temperature range, where both groups of defects were present, the dominant operative conduction mechanism was the variable range hopping conduction mode. Beyond a temperature of about 400 K, the point-like defects started to recover with an activation energy of 90 meV resulting in a decrease in resistivity, independent of the incident ion. The complex-like defects were, therefore, the only remaining group of defects after annealing above 700 K. These latter, thermally stable at least up to 750 K, introduced deep acceptor levels in the bandgap resulting in an increase in the electrical resistivity with higher carrier scattering while keeping the metallic-like behavior of the sample. The generation of both types of defects, as determined by resistivity measurements, appeared to occur through a similar mechanism within a single collision cascade.

Classes of O–D centers in unintentionally and Fe-doped β-Ga2O3 annealed in a D2 ambient

β-Ga2O3 has attracted much recent attention as a promising ultrawide bandgap semiconductor. Hydrogen can affect the conductivity of β-Ga2O3 through the introduction of shallow donors and the passivation of deep acceptors. The introduction of H or D into β-Ga2O3 by annealing in an H2 or D2 ambient at elevated temperature produces different classes of O–H or O–D centers. This work is a study of the interaction of D with VGa1 and VGa2 deep acceptors as well as other impurities and native defects in Ga2O3 by infrared spectroscopy and the complementary theory. (We focus primarily on the deuterium isotope of hydrogen because the vibrational modes of O–D centers can be detected with a higher signal-to-noise ratio than those of O–H.) O–D centers in β-Ga2O3 evolve upon annealing in an inert ambient and are transformed from one type of O–D center into another. These reactions affect the compensation of unintentional shallow donors by deep acceptors that are passivated by D. Defects involving additional impurities in β-Ga2O3 compete with VGa deep acceptors for D and modify the deuterium-related reactions that occur. The defect reactions that occur when D is introduced by annealing in a D2 ambient appear to be simpler than those observed for other introduction methods and provide a foundation for understanding the D-related reactions that can occur in more complicated situations.

A Method to Simulate Extrinsic Light Excitation of Vanadium-Compensated 6H-SiC

Extrinsic light excitation has much lower absorption coefficient compared to intrinsic light excitation, which can better utilize the “bulk” of semiconductor rather than a thin surface as the depth of light absorption is much larger, making it suitable for higher power applications. However, commercial technology computer aided design (TCAD) software has not developed a model for extrinsic light excitation. Therefore, we construct a model of Vanadium-compensated semi-insulating (VCSI) 6H-SiC photoconductive semiconductor switch (PCSS) illuminated with sub-bandgap light, and realize the process of light absorption at V deep acceptor level in Silvaco TCAD simulation by modifying the electron emission rate. Then, we simulate the transient response of 6H-SiC triggered by a nanosecond light pulse and discuss the feasibility of this method.

Ferromagnetism in two-dimensional metal dibromides induced by hole-doping

Using spin-polarized first-principles calculations based on density functional theory, we study the stability, electronic properties and magnetic behavior induced by hole-doping of two-dimensional (2D) PbBr2 and HgBr2. Although inherently nonmagnetic, these materials can exhibit stable ferromagnetic order when hole-doped at densities above a few 1013 cm-2. We also examined the impact of intrinsic and extrinsic defects on inducing hole-doping and subsequent ferromagnetism. Our findings suggest that p-type doping can be achieved by Pb and Hg vacancies and Br antisites, but the latter behaves as deep acceptors. Among the possible dopants we considered, Li substituting Pb or Hg, and S replacing Br in 2D HgBr2, can produce shallow acceptor states near the valence band edges and potentially result in a stable ferromagnetic order in these 2D dibromides.

High resistive buffer layers by Fermi level engineering

An efficient carrier compensation mechanism in semiconductor layers by Fermi-level engineering is demonstrated using the modulation-doping of a deep acceptor and a shallow donor. The punch-through of the depletion region across the whole stack of modulation-doped layers shifts the Fermi level closer toward the midgap position, resulting in the compensation of residual background free carriers. The method represents an alternative to achieve semi-insulating properties in semiconductor materials where a suitable deep acceptor or donor state at the midgap position is not available. We demonstrate the applicability of the concept with a commercially important GaN case study using carbon (deep acceptor) and Si (shallow donor) doping. A strong enhancement of breakdown field strength and reduced charge pileup effects are observed due to the efficient pinning of the Fermi level.

Controllable nitrogen doping of MOCVD Ga2O3 using NH3

We report on the controllable nitrogen doping of β-Ga2O3 as a deep acceptor dopant using ammonia diluted in nitrogen (NH3/N2) as a source of active nitrogen in the metal organic chemical vapor deposition epitaxy. The effects of the NH3/N2 flow rate and substrate temperature on the incorporation efficiency, reproducibility, and controllability of N doping into Ga2O3 were studied using secondary ion mass spectrometry measurements. With the increase in the NH3/N2 molar flow rate from ∼2 × 10−8 to ∼2 × 10−6 mol/min, the N impurities incorporated into the β-Ga2O3 increased linearly from ∼1 × 1018 to ∼2 × 1020 cm−3. At low substrate temperatures (<800 °C), hydrogen was incorporated into the film accompanying nitrogen with comparable concentrations. Despite this, the current–voltage measurements showed that the N and H co-doped films were resistive with a measured resistance of >70 MΩ for a film grown with [N] ≈ [H] of ∼8 × 1018 cm−3. X-ray on-axis (020) and off-axis (111) rocking curve ω-scans and atomic force microscopy measurements show no influence of NH3/N2 dopant on the structural and surface quality of the films. However, the presence of H promoted the growth of (110) and (1¯10) facets elongated along the [001] direction. At high growth temperatures (≥950 °C), the H concentration in the films was reduced by nearly ∼10×, but with a slight increase in the concentration of N. The results show that controllable and repeatable nitrogen doping into β-Ga2O3 can be achieved using ammonia to obtain deep acceptor doping or compensation needed for device engineering in β-Ga2O3-based power electronic devices.

Investigation of carrier transport in ZnO and ZnO:Al thin films sputtered at different oxygen conditions

Undoped and doped zinc oxide in film form is used in a wide range of applications. Its electrical and optical properties depend on the oxide conditions during preparation, which are influenced by many deposition parameters. The aim of this work was to experimentally investigate the properties of films deposited under clearly defined oxygen-rich and oxygen-poor conditions. The observed property changes were then described based on theoretical assumptions about internal defects formed in ZnO under different oxygen conditions. To achieve the objective, the ZnO and ZnO:Al films were sputtered in a mixture of argon and oxygen to ensure oxygen-rich conditions. Oxygen-poor conditions were provided by co-sputtering from oxide and metal targets in argon. We have found that the growth in oxygen-rich conditions leads to approximately stoichiometric ZnO films and the films prepared under oxygen-poor conditions are strongly oxygen deficient. The resistivity of undoped ZnO films can be controlled from 108 to 10−2 Ωcm while maintaining high transparency in the visible spectrum. The high resistivity is caused by the formation of deep acceptors under oxygen-rich conditions. The high concentration of zinc interstitials is responsible for the low resistivity in oxygen poor conditions. Even in the case of ZnO:Al films, the carrier concentration is strongly reduced at oxygen-rich conditions by the deep acceptors. These defects tend to relax during vacuum annealing at 300 °C due to self-diffusion. The carrier mobility is mainly related to the crystallinity. The formation of a high number of basal edge dislocations has been identified as a reason for the reduction in transmittance.

Degradation behavior of CIGS solar Cells: A parametric analysis

A parametric study of the effect of bulk and interface properties on device characteristics as a function of heat and light stress under open-circuit and short-circuit conditions is developed for Cu(In,Ga)(S,Se)2 solar cells using SCAPS-1D simulator. The variables and interdependencies modeled include: (1) conduction band offset (CBO) between buffer and absorber; (2) buffer ionized donor density; (3) CIGS shallow acceptor density; (4) CIGS deep acceptor density; (5) CIGS shallow donor density; (6) ionized acceptor concentration in the ordered vacancy compound (OVC) CIGS/buffer interface; and (7) back contact work-function. An increase in absorber shallow acceptor or a decrease in shallow donor density results in an increase in net carrier density and open-circuit voltage (VOC). A decrease in VOC is observed with an increase in the deep acceptors or neutral midgap defects in the CIGS due to higher charge carrier recombination. A change of CBO from spike to cliff condition is a dominant mechanism of decreasing VOC with an interface defect density of 1012 cm−2. The minimum depletion width is found to be specifically sensitive to CBO and interface defect density. An inflection in the capacitance–voltage curves (in reverse bias) is observed with simultaneous increase in bulk deep acceptor density and shallow donor density near the back contact.

Oxygen doping modulating thermal-activated charge transport of reduced graphene oxide for high performance temperature sensors

Graphene and its derivatives have sparked intense research interest in wearable temperature sensing due to their excellent electric properties, mechanical flexibility, and good biocompatibility. Despite these advantages, the weak temperature dependence of charge transport makes them difficult to achieve a highly sensitive temperature response, which is one of the remaining bottlenecks in the progress towards practical applications. Unfortunately, detailed knowledge about the key factors of the charge transport temperature dependence in this material that determines the critical performance of electrical sensors is very limited up to now. Here, we reveal that oxygen absorption on the ultrathin reduced graphene oxide (RGO) films (∼3 nm) can significantly increase their conductance activation energy over 200% and thus greatly improve the temperature dependence of thermal-activated charge transport. Further investigations suggest that oxygen introduces the deep acceptor states, distributed at an energy level ∼0.175 eV from the valence-band maximum, which allows a highly temperature-dependent impurity ionization process and the resulting vast holes release in a wide temperature range. Remarkably, our temperature sensors based on oxygen-doped ultrathin RGO films show a high sensitivity with temperature conductive coefficient of 14.58% K−1, which is one order of magnitude higher than the reported CNT or graphene-based devices. Moreover, the ultrathin thickness and high thermal conductivity of RGO film allow an ultrafast response time of ∼86 ms, which represents the best level of temperature sensors based on soft materials. Profiting from these advantages, our sensors show good capacity to identify the slight temperature difference of human body, monitor respiratory rate, and detect the environmental temperature. This work not only represents substantial performance advances in temperature sensing, but also provides a new approach to modulate the charge transport temperature dependence, which could be benefited to both device design and fundamental research.

Iridium and gold alloy beta gallium oxide expected to achieve p-type conductivity

The beta monoclinic gallium oxide (β-Ga2O3) is a wide-bandgap material with promising applications in high-power electronics, but bottleneck problem of p-type conductivity has become the biggest obstacle to device performance improvement. The effective p-type doping can be achieved in β-(Ir x Au y Ga1-x-y )2O3 alloys, promising to be synthesised in the laboratory, from an energy perspective. The β-(Ir x Ga1-x )2O3 exhibits an extended valence band with a maximum of 1.94 eV at the edge of the valence band. The location and bandwidth of the extended valence band can be changed with the Ir concentration. The Au substitution at the Ga(2) site actually creates a relatively shallow level, contrary to the expected deep acceptors. The 2p orbital of the O atom easily coupling with the doped atomic orbital to appear as a hole-polaronic state, while the higher energy of the Au-doped hole state avoids coupling with the valence band maximum of the host material. Theoretical feasibility of p-type doping of β-(Ir x Au y Ga1-x-y )2O3 is achieved.