Universal radiation tolerant semiconductor.

Radiation tolerance is determined as the ability of crystalline materials to withstand the accumulation of the radiation induced disorder. Nevertheless, for sufficiently high fluences, in all by far known semiconductors it ends up with either very high disorder levels or amorphization. Here we show that gamma/beta (γ/ß) double polymorph Ga2O3 structures exhibit remarkably high radiation tolerance. Specifically, for room temperature experiments, they tolerate a disorder equivalent to hundreds of displacements per atom, without severe degradations of crystallinity; in comparison with, e.g., Si amorphizable already with the lattice atoms displaced just once. We explain this behavior by an interesting combination of the Ga- and O- sublattice properties in γ-Ga2O3. In particular, O-sublattice exhibits a strong recrystallization trend to recover the face-centered-cubic stacking despite the stronger displacement of O atoms compared to Ga during the active periods of cascades. Notably, we also explained the origin of the ß-to-γ Ga2O3 transformation, as a function of the increased disorder in ß-Ga2O3 and studied the phenomena as a function of the chemical nature of the implanted atoms. As a result, we conclude that γ/ß double polymorph Ga2O3 structures, in terms of their radiation tolerance properties, benchmark a class of universal radiation tolerant semiconductors.

Gettering in PolySi/SiOx Passivating Contacts Enables Si-Based Tandem Solar Cells with High Thermal and Contamination Resilience.

Multijunction solar cells in a tandem configuration could further lower the costs of electricity if crystalline Si (c-Si) is used as the bottom cell. However, for direct monolithic integration on c-Si, only a restricted number of top and bottom cell architectures are compatible, due to either epitaxy or high-temperature constraints, where the interface between subcells is subject to a trade-off between transmittance, electrical interconnection, and bottom cell degradation. Using polySi/SiOx passivating contacts for Si, this degradation can be largely circumvented by tuning the polySi/SiOx stacks to promote gettering of contaminants admitted into the Si bottom cell during the top cell synthesis. Applying this concept to the low-cost top cell chalcogenides Cu2ZnSnS4 (CZTS), CuGaSe2 (CGSe), and AgInGaSe2 (AIGSe), fabricated under harsh S or Se atmospheres above 550 °C, we show that increasing the heavily doped polySi layer thickness from 40 to up to 400 nm prevents a reduction in Si carrier lifetime by 1 order of magnitude, with final lifetimes above 500 µs uniformly across areas up to 20 cm2. In all cases, the increased resilience was correlated with a 99.9% reduction in contaminant concentration in the c-Si bulk, provided by the thick polySi layer, which acts as a buried gettering layer in the tandem structure without compromising the Si passivation quality. The Si resilience decreased as AIGSe > CGSe > CZTS, in accordance with the measured Cu contamination profiles and higher annealing temperatures. An efficiency of up to 7% was achieved for a CZTS/Si tandem, where the Si bottom cell is no longer the limiting factor.

On the permittivity of titanium dioxide.

Conductive rutile TiO2 has received considerable attention recently due to multiple applications. However, the permittivity in conductive, reduced or doped TiO2 appears to cause controversy with reported values in the range 100-10,000. In this work, we propose a method for measurements of the permittivity in conductive, n-type TiO2 that involves: (i) hydrogen ion-implantation to form a donor concentration peak at a known depth, and (ii) capacitance-voltage measurements for donor profiling. We cannot confirm the claims stating an extremely high permittivity of single crystalline TiO2. On the contrary, the permittivity of conductive, reduced single crystalline TiO2 is similar to that of insulating TiO2 established previously, with a Curie-Weiss type temperature dependence and the values in the range 160-240 along with the c-axis.

First-principles calculations of Stark shifts of electronic transitions for defects in semiconductors: the Si vacancy in 4H-SiC.

Point defects in solids are promising single-photon sources with application in quantum sensing, computing and communication. Herein, we describe a theoretical framework for studying electric field effects on defect-related electronic transitions, based on density functional theory calculations with periodic boundary conditions. Sawtooth-shaped electric fields are applied perpendicular to the surface of a two-dimensional defective slab, with induced charge singularities being placed in the vacuum layer. The silicon vacancy (V Si) in 4H-SiC is employed as a benchmark system, having three zero-phonon lines in the near-infrared (V1, V1' and V2) and exhibiting Stark tunability via fabrication of Schottky barrier or p-i-n diodes. In agreement with experimental observations, we find an approximately linear field response for the zero-phonon transitions of V Si involving the decay from the first excited state (named V1 and V2). However, the magnitude of the Stark shifts are overestimated by nearly a factor of 10 when comparing to experimental findings. We discuss several theoretical and experimental aspects which could affect the agreement.

Persistent Double-Layer Formation in Kesterite Solar Cells: A Critical Review.

In kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cell research, an asymmetric crystallization profile is often obtained after annealing, resulting in a bilayered - or double-layered - CZTSSe absorber. So far, only segregated pieces of research exist to characterize the appearance of this double layer, its formation dynamics, and its effect on the performances of devices. In this work, we review the existing research on double-layered kesterites and evaluate the different mechanisms proposed. Using a cosputtering-based approach, we show that the two layers can differ significantly in morphology, composition, and optoelectronic properties and complement the results with a large statistical data set of over 850 individual CZTS solar cells. By reducing the absorber thickness from above 1000 to 300 nm, we show that the double-layer segregation is alleviated. In turn, we see a progressive improvement in the device performance for lower thickness, which alone would be inconsistent with the well-known case of ultrathin CIGS solar cells. We therefore attribute the improvements to the reduced double-layer occurrence and find that the double layer limits the efficiency of our devices to below 7%. By comparing the results with CZTS grown on monocrystalline Si substrates, without a native Na supply, we show that the alkali metal supply does not determine the double-layer formation but merely reduces the threshold for its occurrence. Instead, we propose that the main formation mechanism is the early migration of Cu to the surface during annealing and formation of Cu2-xS phases in a self-regulating process akin to the Kirkendall effect. Finally, we comment on the generality of the mechanism proposed by comparing our results to other synthesis routes, including our own in-house results from solution processing and pulsed laser deposition of sulfide- and oxide-based targets. We find that although the double-layer occurrence largely depends on the kesterite synthesis route, the common factors determining the double-layer occurrence appear to be the presence of metallic Cu and/or a chalcogen deficiency in the precursor matrix. We suggest that understanding the limitations imposed by the double-layer dynamics could prove useful to pave the way for breaking the 13% efficiency barrier for this technology.

Transition-Metal Oxides for Kesterite Solar Cells Developed on Transparent Substrates.

Fabrication on transparent soda-lime glass/fluorine-doped tin oxide (FTO) substrates opens the way to advanced applications for kesterite solar cells such as semitransparent, bifacial, and tandem devices, which are key to the future of the PV market. However, the complex behavior of the p-kesterite/n-FTO back-interface potentially limits the power conversion efficiency of such devices. Overcoming this issue requires careful interface engineering. This work empirically explores the use of transition-metal oxides (TMOs) and Mo-based nanolayers to improve the back-interface of Cu2ZnSnSe4, Cu2ZnSnS4, and Cu2ZnSn(S,Se)4 solar cells fabricated on transparent glass/FTO substrates. Although the use of TMOs alone is found to be highly detrimental to the devices inducing complex current-blocking behaviors, the use of Mo:Na nanolayers and their combination with n-type TMOs TiO2 and V2O5 are shown to be a very promising strategy to improve the limited performance of kesterite devices fabricated on transparent substrates. The optoelectronic, morphological, structural, and in-depth compositional characterization performed on the devices suggests that the improvements observed are related to a combination of shunt insulation and recombination reduction. This way, record efficiencies of 6.1, 6.2, and 7.9% are obtained for Cu2ZnSnSe4, Cu2ZnSnS4, and Cu2ZnSn(S,Se)4 devices, respectively, giving proof of the potential of TMOs for the development of kesterite solar cells on transparent substrates.

Formation of N2 bubbles along grain boundaries in (ZnO)1-x(GaN)x: nanoscale STEM-EELS studies.

Direct evidence of N2 formation after annealing of (ZnO)1-x(GaN)x alloys was revealed. N2 was trapped by VZn+Ga-clusters, forming faceted voids along grain boundaries. This study shows that N-N bonding is a competitive path for nitrogen after annealing, in addition to the increasing Ga-N bonds, indicating that N in O substitution sites (NO) is not a stable configuration.

Role of Nitrogen in Defect Evolution in Zinc Oxide: STEM-EELS Nanoscale Investigations.

Direct evidence of the formation of nitrogen molecules (N2) after ion implantion of ZnO has been revealed by an atomically resolved scanning transmission electron microscopy (STEM)-electron energy-loss spectroscopy (EELS) investigation. Taking advantage of the possibility of using multiple detectors simultaneously in aberration-corrected STEM, we utilize the detailed correlation between the atomic structure and chemical identification to develop a model explaining the formation and evolution of different defect types and their interaction with N. In particular, the formation of zinc vacancy (VZn) clusters filled with N2 after heat treatment at 650 °C was observed, clearly indicating that N has not been stabilized in the O substitution site, thus limiting p-type doping. Previous results showing an exceptional thermal stability of vacancy clusters only for the case of N-doped ZnO are supported. Furthermore, VZn-N2 stabilization leads to suppression of VZn-Zni recombination; hence, the highly mobile Zn interstitials preferentially condense on the basal planes promoting formation of extended defects (basal stacking faults and stacking mismatched boundaries). The terminations of these defects provide energetically favorable sites for further N2 trapping as a way to reduce local strain fields.

ZnCr2O4 Inclusions in ZnO Matrix Investigated by Probe-Corrected STEM-EELS.

The ZnCr2O4/ZnO materials system has a wide range of potential applications, for example, as a photocatalytic material for waste-water treatment and gas sensing. In this study, probe-corrected high-resolution scanning transmission electron microscopy and geometric phase analysis were utilized to study the dislocation structure and strain distribution at the interface between zinc oxide (ZnO) and embedded zinc chromium oxide (ZnCr2O4) particles. Ball-milled and dry-pressed ZnO and chromium oxide (α-Cr2O3) powder formed ZnCr2O4 inclusions in ZnO with size ~400 nm, where the interface properties depended on the interface orientation. In particular, sharp interfaces were observed for ZnO [2113]/ZnCr2O4 [110] orientations, while ZnO [1210]/ZnCr2O4 [112] orientations revealed an interface over several atomic layers, with a high density of dislocations. Further, monochromated electron energy-loss spectroscopy was employed to map the optical band gap of ZnCr2O4 nanoparticles in the ZnO matrix and their interface, where the average band gap of ZnCr2O4 nanoparticles was measured to be 3.84 ± 0.03 eV, in contrast to 3.22 ± 0.01 eV for the ZnO matrix.

Highly Correlated Hydride Ion Tracer Diffusion in SrTiO3- xH x Oxyhydrides.

Mixed oxide hydride anion systems constitute a novel class of materials exhibiting intriguing properties such as solid-state hydride ion conduction and fast anion exchange. In this contribution we derive the kinetics of hydride ion transport in a mixed oxide-hydride system, SrTiO3- xH x, through isotope exchange and depth profiling. Density functional theory (DFT) calculations indicate that migration of H- to neighboring vacant oxygen lattice sites is fast, but that long-range transport is impeded by slow reorganization of the oxygen sublattice. From measured hydride tracer-diffusion coefficients and the correlation factors derived from DFT, we are able to derive the hydrogen self-diffusion coefficients in SrTiO3- xH x. More generally, the explicit description of hydride ion transport in SrTiO3- xH x through combination of experimental and computational methods reported in this work can be applied to explore anion diffusion in other mixed anion systems.

Structural and optical properties of individual Zn2GeO4 particles embedded in ZnO.

Functionalizing transparent conducting oxides (TCOs) is an intriguing approach to expand the tunability and operation of optoelectronic devices. For example, forming nanoparticles that act as quantum wells or barriers in zinc oxide (ZnO), one of the main TCOs today, may expand its optical and electronic tunability. In this work, 800 keV Ge ions have been implanted at a dose of 1 × 1016 cm-2 into crystalline ZnO. After annealing at 1000 °C embedded disk-shaped particles with diameters up to 100 nm are formed. Scanning transmission electron microscopy shows that these are particles of the trigonal Zn2GeO4 phase. The particles are terminated by atomically sharp facets of the type {11 [Formula: see text] 0}, and the interface between the matrix and particles is decorated with misfit dislocations in order to accommodate the lattice mismatch between the two crystals. Electron energy loss spectroscopy has been employed to measure the band gap of individual nanoparticles, showing an onset of band-to-band transitions at 5.03 ± 0.02 eV. This work illustrates the advantages of using STEM characterization methods, where information of structure, growth, and properties can be directly obtained.

Diffusivity of the double negatively charged mono-vacancy in silicon.

Lightly-doped silicon (Si) samples of n-type conductivity have been irradiated with 2.0 MeV [Formula: see text] ions at a temperature of 30 K and characterized in situ by deep level transient spectroscopy (DLTS) measurements using an on-line setup. Migration of the Si mono-vacancy in its double negative charge state (V 2-) starts to occur at temperatures above ∼70 K and is monitored via trapping of V 2- by interstitial oxygen impurity atoms ([Formula: see text]), leading to the growth of the prominent vacancy-oxygen ([Formula: see text]) center. The [Formula: see text] center gives rise to an acceptor level located at ∼0.17 eV below the conduction band edge (E c ) and is readily detected by DLTS measurements. Post-irradiation isothermal anneals at temperatures in the range of 70 to 90 K reveal first-order kinetics for the reaction [Formula: see text] in both Czochralski-grown and Float-zone samples subjected to low fluences of [Formula: see text] ions, i.e. the irradiation-induced V concentration is dilute ([Formula: see text]1013 cm-3). On the basis of these kinetics data and the content of [Formula: see text], the diffusivity of V 2- can be determined quantitatively and is found to exhibit an activation energy for migration of ∼0.18 eV with a pre-exponential factor of ∼[Formula: see text] cm2 s-1. The latter value evidences a simple jump process without any entropy effects for the motion of V 2-. No deep level in the bandgap to be associated with V 2- is observed but the results suggest that the level is situated deeper than ∼0.19 eV below E c , corroborating results reported previously in the literature.

Ultra-doped n-type germanium thin films for sensing in the mid-infrared.

A key milestone for the next generation of high-performance multifunctional microelectronic devices is the monolithic integration of high-mobility materials with Si technology. The use of Ge instead of Si as a basic material in nanoelectronics would need homogeneous p- and n-type doping with high carrier densities. Here we use ion implantation followed by rear side flash-lamp annealing (r-FLA) for the fabrication of heavily doped n-type Ge with high mobility. This approach, in contrast to conventional annealing procedures, leads to the full recrystallization of Ge films and high P activation. In this way single crystalline Ge thin films free of defects with maximum attained carrier concentrations of 2.20 ± 0.11 × 10(20) cm(-3) and carrier mobilities above 260 cm(2)/(V·s) were obtained. The obtained ultra-doped Ge films display a room-temperature plasma frequency above 1,850 cm(-1), which enables to exploit the plasmonic properties of Ge for sensing in the mid-infrared spectral range.

Intrinsic point-defect balance in self-ion-implanted ZnO.

The role of excess intrinsic atoms for residual point defect balance has been discriminated by implanting Zn or O ions into Li-containing ZnO and monitoring Li redistribution and electrical resistivity after postimplant anneals. Strongly Li-depleted regions were detected in the Zn-implanted samples at depths beyond the projected range (R(p)) upon annealing ≥ 600 °C, correlating with a resistivity decrease. In contrast, similar anneals of the O-implanted samples resulted in Li accumulation at R(p) and an increased resistivity. Control samples implanted with Ar or Ne ions, yielding similar defect production as for the Zn or O implants but with no surplus of intrinsic atoms, revealed no Li depletion. Thus, the depletion of Li shows evidence of excess Zn interstitials (Zn(I)) being released during annealing of the Zn-implanted samples. These Zn(I)'s convert substitutional Li atoms (Li(Zn)) into highly mobile interstitial ones leading to the strongly Li-depleted regions. In the O-implanted samples, the high resistivity provides evidence of stable O(I)-related acceptors.