The concentration of vacancies and impurities in semiconductors plays a crucial role in determining their electrical, optical, and thermal properties. This study aims to clarify the nature of the interaction between positrons and ionized p-type impurities, emphasizing the similarities they share with the interaction between holes and this type of impurity. An overall strategy for investigating defects in semiconductor crystals that exhibit a combination of vacancies and p-type impurities is presented. By using positron annihilation spectroscopy, in particular, Doppler broadening of the annihilation radiation, we quantify the concentration of vacancies in epitaxial Si crystals grown by low-energy plasma-enhanced chemical vapor deposition. The vacancy number densities that we find are (1.2 ± 1.0) × 1017 cm−3 and (3.2 ± 1.5) × 1020 cm−3 for growth rates of 0.27 and 4.9 nm/s, respectively. Subsequent extended annealing of the Si samples effectively reduces the vacancy density below the sensitivity threshold of the positron technique. Secondary ion mass spectrometry indicates that the boron doping remains unaffected during the annealing treatment intended for vacancy removal. This study provides valuable insights into the intricate interplay between vacancies and ionized impurities with positrons in semiconductor crystals. The obtained results contribute to advance the control and understanding of material properties in heterostructures by emphasizing the significance of managing vacancy and dopant concentrations.
Isolated, micro-metre sized diamonds are grown by micro-wave plasma chemical vapour deposition technique on Si(001) substrates. Each diamond is uniquely identified by markers milled in the Si substrate by Ga+focused ion beam. The morphology and micro-grain structure analysis, indicates that the diamonds are icosahedral or bi-crystals. Icosahedral diamonds have higher (up toσh= 2.3 GPa), and wider distribution (Δσh= 4.47 GPa) of hydrostatic stress built up at the micro-crystal grain boundaries, compared to the other crystals. The number and spectral shape of SiV-colour centres incorporated in the micro-diamonds (MDs) is analysed, and estimated by means of temperature dependent photoluminescence measurements, and Monte Carlo simulations. The Monte Carlo simulations indicates that the number of SiV-colour centres is a few thousand per MD.
Given the recent increase in the demand for gallium nitride (GaN) in different markets like optoelectronics and power devices, the request for epitaxially grown GaN will further increase. To meet this high demand, higher throughput and more economical manufacturing technologies must be advanced. In this work, GaN thin films are deposited by reactive sputter deposition from a liquid gallium target at a substrate temperature of 900 °C. The layers are grown epitaxially on c-plane oriented sapphire in an industrial-scale sputter tool from Evatec AG. Due to the growth rate of >1 nm/s and the fast substrate heat-up time, the throughput in a production setup can be increased compared to other GaN growth techniques. The resistivity of the intrinsic insulating GaN can be lowered by intentional Si doping during the sputter deposition process by three orders of magnitude. Thereby, conductive n-type GaN can be grown with different dopant amounts. The carrier mobility of the sputter deposited film is 45 cm2 V−1 s−1 at a carrier concentration of 1.1 × 1020 cm−3 based on room temperature Hall measurements using a van der Pauw geometry. The lowest resistivity reaches 1300 μΩ cm, which is confirmed by sheet resistance measurements. Undoped films exhibit an x-ray diffraction rocking curve full width at half maximum of 0.2°, which increases up to 0.5° for highly Si-doped layers. The presented results show that GaN prepared by reactive sputter deposition from a liquid gallium source is a viable alternative to conventional deposition techniques for GaN.
This work presents a new approach suitable for mapping reciprocal space in three dimensions with standard laboratory equipment and a typical X-ray diffraction setup. The method is based on symmetric and coplanar high-resolution X-ray diffraction, ideally realized using 2D X-ray pixel detectors. The processing of experimental data exploits the Radon transform commonly used in medical and materials science. It is shown that this technique can also be used for diffraction mapping in reciprocal space even if a highly collimated beam is not available. The application of the method is demonstrated for various types of epitaxial microcrystals on Si substrates. These comprise partially fused SiGe microcrystals that are tens of micrometres high, multiple-quantum-well structures grown on SiGe microcrystals and pyramid-shaped GaAs/Ge microcrystals on top of Si micropillars.
Surface-enhanced Raman spectroscopy (SERS) technology is an attractive method for the prompt and accurate on-site screening of illicit drugs. As portable Raman systems are available for on-site screening, the readiness of SERS technology for sensing applications is predominantly dependent on the accuracy, stability and cost-effectiveness of the SERS strip. An atmospheric-pressure plasma-assisted chemical deposition process that can deposit an even distribution of nanogold particles in a one-step process has been developed. The process was used to print a nanogold film on a paper-based substrate using a HAuCl4 solution precursor. X-ray photoelectron spectroscopy (XPS) analysis demonstrates that the gold has been fully reduced and that subsequent plasma post-treatment decreases the carbon content of the film. Results for cocaine detection using this substrate were compared with two commercial SERS substrates, one based on nanogold on paper and the currently available best commercial SERS substrate based on an Ag pillar structure. A larger number of bands associated with cocaine was detected using the plasma-printed substrate than the commercial substrates across a range of cocaine concentrations from 1 to 5000 ng/mL. A detection limit as low as 1 ng/mL cocaine with high spatial uniformity was demonstrated with the plasma-printed substrate. It is shown that the plasma-printed substrate can be produced at a much lower cost than the price of the commercial substrate.
In this paper, a novel approach is presented to tailor the stress properties of diamond thin films via boron doping and micro-fabrication of bridges using focused ion beam milling. The experimental data, based on detailed confocal micro-Raman investigations, are supported and interpreted through finite element method calculations of the stress distribution at mechanical equilibrium. These results indicate that appropriate design of microbridge geometries, together with boron doping, would allow the material stress to be largely enhanced or diminished compared to non-patterned thin films. Our approach, together with a deterministic incorporation and positioning of diamond color centers, may open novel opportunities to tailor the optical and spin properties of diamond-based quantum devices through stress engineering.
The synthesis of graphene on cubic silicon carbide on silicon pseudosubstrates draws enormous interest due to the potential integration of the 2D material with the well-established silicon technology and processing. However, the control of transport properties over large scales on this platform, essential for integrated electronics and photonics applications, has lagged behind so far, due to limitations such as 3C-SiC/Si interface instability and nonuniform graphene coverage. We address these issues by obtaining an epitaxial graphene (EG) onto 3C-SiC on a highly resistive silicon substrate using an alloy-mediated, solidsource graphene synthesis. We report the transport properties of EG grown over large areas directly on 3C-SiC(100) and 3C-SiC(111) substrates, and we present the corresponding physical models. We observe that the carrier transport of EG/3C-SiC is dominated by the graphene-substrate interaction rather than the EG grain size, sharing the same conductivity and same inverse power law as EG on 4H- or 6H-SiC(0001) substrates- although the grain sizes for the latter are vastly different. In addition, we show that the induced oxidation/silicates at the EG/3C-SiC interface generate a p-type charge in this graphene, particularly high for the EG/3C-SiC(001). When silicates are at the interface, the presence of a buffer layer in the EG/3C-SiC(111) system is found to reduce somewhat the charge transfer. This work also indicates that a renewed focus on the understanding and engineering of the EG interfaces could very well enable the long sought-after graphene-based electronics and photonics integrated on silicon.
RuO2 thin films were prepared using magnetron sputtering under different deposition conditions, including direct current (DC) and radio frequency (RF) discharges, metallic/oxide cathodes, different substrate temperatures, pressures, and deposition times. The surface morphology, residual stress, composition, crystal structure, mechanical properties, and pH performances of these RuO2 thin films were investigated. The RuO2 thin films RF sputtered from a metallic cathode at 250 °C exhibited good pH sensitivity of 56.35 mV/pH. However, these films were rougher, less dense, and relatively softer. However, the DC sputtered RuO2 thin film prepared from an oxide cathode at 250 °C exhibited a pH sensitivity of 57.37 mV/pH with a smoother surface, denser microstructure and higher hardness. The thin film RF sputtered from the metallic cathode exhibited better pH response than those RF sputtered from the oxide cathode due to the higher percentage of the RuO3 phase present in this film.
The atomic structure of grain boundaries in Ge micro-crystals grown on Si pillars for the fabrication of a monolithically integrated X-ray detector was studied by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Three different boundaries are found in Ge: Σ3{111} coherent twin boundaries, Σ3{112} incoherent twin boundaries, and Σ9{122} and Σ27{552} grain boundaries. They are described using the structural unit models containing single columns. Remarkably, we find for the first time a Σ3{112} incoherent twin boundary exhibiting two different atomic structures; one symmetric and one asymmetric. Their co-occurrence is explained by the presence of a small step in the boundary plane and the introduction of dislocations. Likewise, the atomic structure of junctions formed by the interaction of twin boundaries which result in Σ9{122} and Σ27{552} grain boundaries is also revealed. Geometrical phase analysis is applied to map the strain fields at two triple junctions and to uncover the position of the dislocations.
The performance of X-ray imaging detectors based on epitaxial Ge-crystal arrays grown on patterned Si substrates is severely limited by the presence of misfit and threading dislocations. Here, we study the effect of cyclic thermal annealing on misfit dislocations at the Ge/Si interface. By scanning transmission electron microscopy and energy dispersive X-ray spectroscopy, it is shown that the annealing process promotes the diffusion of Si into the Ge crystal resulting in a corrugated interface and slightly reduces the dislocation density. Finally, our results demonstrate that the thermal process is very effective at eliminating twin boundaries.
Ge vertical heterostructures grown on deeply-patterned Si(001) were first obtained in 2012 (C.V. Falub et al., Science2012, 335, 1330–1334), immediately capturing attention due to the appealing possibility of growing micron-sized Ge crystals largely free of thermal stress and hosting dislocations only in a small fraction of their volume. Since then, considerable progress has been made in terms of extending the technique to several other systems, and of developing further strategies to lower the dislocation density. In this review, we shall mainly focus on the latter aspect, discussing in detail 100% dislocation-free, micron-sized vertical heterostructures obtained by exploiting compositional grading in the epitaxial crystals. Furthermore, we shall also analyze the role played by the shape of the pre-patterned substrate in directly influencing the dislocation distribution.
Epitaxial growth of dissimilar materials on patterned substrates is a promising technique for defect-free, monolithic integration of various optoelectronic devices on a single chip. In this work we investigate the structural quality of Ge microcrystal arrays monolithically grown at temperatures ranging from 450 to 575°C on patterned Si substrates. Using high resolution X-ray diffraction with reciprocal space mapping, we obtain the lattice parameters, strain and degree of relaxation. This structural analysis gives us insight in dislocation formation together with quantitative information about thermal relaxation and lattice bending.
The scanning X-ray nanodiffraction technique is used to reconstruct the three-dimensional distribution of lattice strain and Ge concentration in compositionally graded Si 1− x Ge x microcrystals grown epitaxially on Si pillars. The reconstructed crystal shape qualitatively agrees with scanning electron micrographs and the calculated three-dimensional distribution of lattice tilt quantitatively matches finite-element method simulations. The grading of the Ge content obtained from reciprocal-space maps corresponds to the nominal grading of the epitaxial growth recipe. The X-ray measurements confirm strain calculations, according to which the lattice curvature of the microcrystals is dominated by the misfit strain, while the thermal strain contributes negligibly. The nanodiffraction experiments also indicate that the strain in narrow microcrystals on 2 × 2 µm Si pillars is relaxed purely elastically, while in wider microcrystals on 5 × 5 µm Si pillars, plastic relaxation by means of dislocations sets in. This confirms previous work on these structures using transmission electron microscopy and defect etching.
We study covalent bonds between p-doped Si wafers (resistivity ∼10 Ω cm) fabricated on a recently developed 200 mm high-vacuum system. Oxide- and void free interfaces were obtained by argon (Ar) or neon (Ne) sputtering prior to wafer bonding at room temperature. The influence of the sputter induced amorphous Si layer at the bonding interface on the electrical behavior is accessed with temperature-dependent current-voltage measurements. In as-bonded structures, charge transport is impeded by a potential barrier of 0.7 V at the interface with thermionic emission being the dominant charge transport mechanism. Current-voltage characteristics are found to be asymmetric which can tentatively be attributed to electric dipole formation at the interface as a result of the time delay between the surface preparation of the two bonding partners. Electron beam induced current measurements confirm the corresponding asymmetric double Schottky barrier like band-alignment. Moreover, we demonstrate that defect annihilation...
We present a joint theoretical and experimental analysis of the dislocation distribution in graded epitaxial SiGe crystals grown on under-etched Si pillars by low-energy plasma-enhanced chemical vapor deposition. Dislocation dynamics simulations are used to investigate preferential positioning of ${60}^{\ensuremath{\circ}}$ dislocations introduced in the system to release the lattice misfit strain. Coupling to a finite-element solver is exploited to allow for the exact numerical treatment of the stress fields in the presence of a complex distribution of free surfaces. The results show that, by suitably under-etching the Si pillars, it is possible to reverse the sign of the Burgers vector of the dislocations. This helps explaining differences in the experimentally observed distribution of dislocations in SiGe crystals grown on vertical and under-etched pillars, leading to a strong reduction of defects in the latter case. The agreement between simulations and experiments is not simply qualitative: the predicted number of defects generated by multiplication processes in tall crystals is indeed fully consistent with the measured one.
In this work we present an innovative approach to realise coherent, highly-mismatched 3-dimensional heterostructures on substrates patterned at the micrometre-scale. The approach is based on the out-of-equilibrium deposition of SiGe alloys graded at an exceptionally shallow grading rate (GR) of 1.5%µm−1 by low energy plasma enhanced chemical vapour deposition (LEPECVD). Fully coherent SiGe/Si crystals up to 6µm in width were achieved as confirmed by defect etching and transmission electron microscopy (TEM) analyses. The experimental results are supported by calculations of the energy for dislocation formation which indicate that elastic relaxation is energetically favoured over plastic relaxation in the narrower heterostructures. X-ray diffraction measurements show that the SiGe crystals are strain-free irrespective of the stress relieving mechanism which changes from elastic to plastic by increasing their width. The impact of dislocations on the SiGe crystal quality is analysed by comparing the width of X-ray diffraction peaks as a function of the heterostructure size.
2 h110i in three dimensional Ge crystals grown on (001)-Si substrates Y. Arroyo Rojas Dasilva, M. D. Rossell, D. Keller, P. Gr€ oning, F. Isa, T. Kreiliger, H. von K€ anel, G. Isella, and R. Erni Electron Microscopy Center, EMPA, Swiss Federal Laboratories for Materials Science and Technology, D€ ubendorf, Switzerland Laboratory for Thin Films and Photovoltaics, EMPA, Swiss Federal Laboratories for Materials Science and Technology, D€ ubendorf, Switzerland Advanced Materials and Surfaces, EMPA, Swiss Federal Laboratories for Materials Science and Technology, D€ ubendorf, Switzerland Solid State Physics Laboratory, ETH, Zurich, Switzerland L-NESS and Department of Physics, Politecnico di Milano, Como, Italy