Search

The electronic band alignment of an alumina/zinc oxide thin-film heterostructure solely grown by atomic layer deposition has been determined by XPS/UPS depth profiling, correlating the electronic properties with the interface chemical composition.

Energy harvesting for Internet of Things applications, comprising sensing, life sciences, wearables, and communications, requires efficient thermoelectric (TE) materials, ideally semiconductors compatible with Si technology. In this work, we investigate the potential of GeSn/Ge layers, a group IV material system, as TE material for low-grade heat conversion. We extract the lattice thermal conductivity, by developing an analytical model based on Raman thermometry and heat transport model, and use it to predict thermoelectric performances. The lattice thermal conductivity decreases from 56 W/(m·K) for Ge to 4 W/(m·K) by increasing the Sn atomic composition to 14%. The bulk cubic Ge0.86Sn0.14 alloy features a TE figure of merit of ZT ∼ 0.4 at 300 K and an impressive 1.04 at 600 K. These values are extremely promising in view of the use of GeSn/Ge layers operating in the typical on-chip temperature range.

Three-dimensional (3D) self-ordered Ge nanodots in cyclic epitaxial growth of Ge/SiGe superlattice on Si0.4Ge0.6 virtual substrate (VS) were fabricated by reduced pressure chemical vapor deposition. The Ge nanodots were formed by Stranski-Krastanov mechanism. By the Ge/SiGe superlattice deposition, dot-on-dot alignment and 〈100〉 alignment were obtained toward the vertical and lateral direction, respectively. Facets and growth mechanism of Ge nanodots and key factors of alignment were studied. Two types of Ge nanodots were observed, diamond-like nanodots composed of {105} and dome-like nanodots composed of {113} and {519} or {15 3 23} facets. The Ge nanodots tend to grow directly above the nanodots of the previous period as these regions show a relatively higher tensile strain induced by the buried nanodots. Thus, this dot-on-dot alignment is sensitive to the SiGe spacer thickness, and it degrades when the SiGe spacer becomes thicker. The Ge content of the SiGe spacer ranging from 45 to 52% affects the lateral alignment and the size uniformity of Ge nanodots because of the strain balance between the superlattice and the VS. By maintaining the strain balance, ordering of the 3D aligned Ge nanodots can be improved.

n-type Ge/SiGe asymmetric coupled quantum wells represent the building block of a variety of nanoscale quantum devices, including recently proposed designs for a silicon-based THz quantum cascade laser. In this paper, we combine structural and spectroscopic experiments on 20-module superstructures, each featuring two Ge wells coupled through a Ge-rich SiGe tunnel barrier, as a function of the geometry parameters of the design and the P dopant concentration. Through a comparison of THz spectroscopic data with numerical calculations of intersubband optical absorption resonances, we demonstrated that it is possible to tune, by design, the energy and the spatial overlap of quantum confined subbands in the conduction band of the heterostructures. The high structural/interface quality of the samples and the control achieved on subband hybridization are promising starting points towards a working electrically pumped light-emitting device.

Indium oxide (InxOy) thin films were deposited by plasma-enhanced atomic layer deposition (PEALD) using trimethylindium and oxygen plasma in a low-temperature range of 80–200 °C. The optical properties, chemical composition, crystallographic structure, and electrical characteristics of these layers were investigated by spectroscopic ellipsometry (SE), x-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), as well as current-voltage and capacitance-voltage measurements. The SE results yielded a nearly constant growth rate of 0.56 A per cycle and a thickness inhomogeneity of ≤1.2% across 4-in. substrates in the temperature range of 100–150 °C. The refractive index (at 632.8 nm) was found to be 2.07 for the films deposited at 150 °C. The PEALD-InxOy layers exhibit a direct (3.3 ± 0.2 eV) and an indirect (2.8 ± 0.1 eV) bandgap with an uptrend for both with increasing substrate temperature. Based on XPS characterization, all InxOy samples are free of carbon impurities and show a temperature-dependent off-stoichiometry indicating oxygen vacancies. XRD diffraction patterns demonstrate an onset of crystallization at 150 °C. Consistent with the optical, XPS, and XRD data, the films deposited at ≥150 °C possess higher electrical conductivity. Our findings prove that a low-temperature PEALD process of InxOy is feasible and promising for a high-quality thin-film deposition without chemical impurities on thermally fragile substrates.

The imaging and sensing technology operating in the THz region of the electromagnetic spectrum has a number of applications, with demonstrator products already available on the market for oncology imaging, production monitoring, and non-destructive test [1]. However, the THz sources now at hand are still bulky and too expensive for expanding this technology to other proposed applications, which also include, among other, THz bandwidth photonics and security imaging. A higher level of integration with control electronics, a lower production cost, and a broader wavelength range of emission towards the far-infrared, are all desirable features to expand the fields of application of THz radiation. N-type Ge/SiGe quantum cascade structures grown on top of a Si(001) substrate are particularly promising for realizing a Si based THz source [2]. The low effective mass and long non-radiative relaxation times due to the non-polar nature of the material, are expected to i) provide gain values close to those demonstrated in III-V quantum cascade structures at 4 K, and ii) to potentially enable 300 K operation. In this presentation we will discuss the optical and structural properties of n-type s-Ge/SiGe multi-quantum wells and asymmetric coupled quantum wells grown on Si(001) substrates by means of ultrahigh vacuum chemical vapor deposition [3]. Extensive structural characterization obtained by scanning transmission electron microscopy (STEM), atomic probe tomography (APT) and X-ray diffraction shows the high material quality of strain-symmetrized structures (up to 5 micron active region thickness) and heterointerfaces (featuring interface roughness below 0.2 nm), down to the ultrathin barrier limit (about 1 nm). By performing THz absorption spectroscopy measurements combined to theoretical modeling on different asymmetric coupled quantum well systems (with varying large-well width or barrier thickness), we unambiguously demonstrated inter-well coupling and wavefunction tunneling [3]. The agreement between experimental data and simulations allowed us to characterize the tunneling barrier parameters and, in turn, achieve a highly-controlled engineering of the electronic structure in forthcoming unipolar cascade systems based on n-type Ge/SiGe multi quantum-wells. Furthermore, by pump-and-probe, and time domain spectroscopic data with a thorough theoretical modeling, we will show that this material system is indeed promising as active material in quantum cascade lasers (QCL). We found i) narrow intersubband (ISB) absorption lines; ii) relatively long non-radiative ISB relaxation times at high temperature; iii) relaxation times for different ISB transitions favorable to population inversion. Leveraging on the promising results obtained by spectroscopy experiments, we theoretically investigate an electrically-pumped Ge/SiGe THz QCL through a non-Equilibrium Green Function formalism (nextnano.QCL), using as material parameters to model the scattering processes the values estimated from the analysis of the optical experimental data [4]. As expected, due to the weaker interaction with the phonon field with respect to III-V based devices, we find a lower impact of the temperature on the gain spectrum. In addition, simulations show that the interface roughness values measured on our samples allows to achieve gain overcoming the losses of double-metal waveguides at room temperature. We believe that the present results will motivate new experimental efforts aimed at demonstrating room-temperature operation in group IV QCL THz devices. References [1] D. J. Paul, Laser Photon. Rev. 4, 610 (2010). [2] K. Driscoll, and R. Paiella, J. Appl. Phys. 102, 093103 (2007). [3] C. Ciano, M. Virgilio, M. Montanari, L. Persichetti, L. Di Gaspare, M. Ortolani, L. Baldassarre, M. H. Zollner, O. Skibitzki, G.Scalari, J. Faist, D. J. Paul, M. Scuderi, G. Nicotra, T. Grange, S. Birner, G. Capellini, and M. De Seta, Accepted in Phys. Rev. Appl., 11, 014003 (2019). [4] T. Grange, D. Stark, G. Scalari, J. Faist, L. Persichetti, L. Di Gaspare, M. De Seta, M. Ortolani, D.J. Paul, G. Capellini, S. Birner and M. Virgilio, Submitted to Applied Physics Letters. Preprint available at https://arxiv.org/pdf/1811.12879.pdf.

InGaN/GaN double heterostructures and multiquantum wells (MQWs) have been successfully developed since more than 20 years for LED lightning applications. Recent developments show that state-of-the-art LEDs benefit from artificially generated V-pit defects. However, the control of structural and chemical properties plays a tremendous role. In this paper, we report on the lateral distribution of V-pit defects and photoluminescence of InGaN/GaN MQWs grown on thick GaN on patterned sapphire substrates. The synchrotron-based scanning X-ray diffraction microscopy technique K-map was employed to locally correlate these properties with the local tilt, strain, and composition of the InGaN/GaN MQW. Compositional fluctuation is the main factor for the variation of photoluminescence intensity and broadening. In turn, V-pit defects align along small-angle grain boundaries and their strain fields are identified as a reason for promoting the InGaN segregation process on a microscale.

Regular surface undulations, called cross-hatch patterns, appearing at the free surface of lattice-mismatched heteroepitaxial films are a key signature of plastic relaxation. Here we show that the dynamics of cross-hatch formation is accurately described by a continuum model based on strain-mediated surface diffusion, provided that a realistic distribution of dislocations is considered. We demonstrate quantitative agreement between our time-dependent simulations and dedicated atomic force microscopy experiments on ${\mathrm{Si}}_{0.92}{\mathrm{Ge}}_{0.08}$ films grown on Si(001) at various thicknesses, finally shedding light on the origin and on the dynamical behavior of a widely investigated pattern, first observed more than half a century ago.

We provide an in-depth characterization of the dislocation distribution in partially relaxed Si0.92Ge0.08/Si(001) films. This is achieved by an innovative and general method, combining two state-of-the-art characterization techniques through suitable modeling. After having inferred the dislocation positions from transmission-electron-microscopy images, we theoretically reproduce scanning-x-ray-diffraction-microscopy tilt maps measured on the very same region of the sample. We obtain a nearly perfect match between model predictions and experimental data. As a result, we claim that it is possible to establish a local, direct correlation between the dislocations revealed by the transmission-electron-microscopy analysis and the measured lattice tilt distribution.

The journal of physical chemistry / C 118(6), 3056 - 3061(2014). doi:10.1021/jp4082917, The structural changes of ultrathin PrO$_2$(111) films grown on Si(111) due to thermal reduction in ultra high vacuum are investigated. Therefore, praseodymia films are treated with oxygen plasma to obtain completely oxidized PrO$_2$ films. The reduction of these films is studied with thermal desorption spectroscopy combined with ex situ X-ray diffraction measurements. It is shown that the distinct desorption peaks of molecular oxygen are correlated with stabilization of several intermediate phases of praseodymia. The most intense signal of desorbing oxygen is observed at ∼650 K. It is coupled to the strongest impact on the crystalline structure since we observe the transition PrO$_2$ → Pr$_5$O$_9$. Further oxygen desorption leads to additional phase transitions with laterally coexisting phases. Grazing incidence X-ray diffraction measurements reveal that the initial pinning to the lateral lattice constant of hexagonal Pr$_2$O$_3$(0001) is not breached due to the plasma treatment. This hexagonal pinning is released during the oxygen desorption so that the crystalline structure of the praseodymia films does not only expand vertically but also laterally., Published by Soc., Washington, DC

The inherent properties of epitaxial oxide thin-film layers have attracted the intense interest of different research fields, such as catalysis and microelectronics. The focus of this work is the temperature-dependent oxygen release, oxygen vacancy formation, and lattice rearrangement of Ce1–xPrxO2−δ thin films with systematic stoichiometry variation (x = 0–1) and oxygen deficiency (δ > 0) on Si(111). The mixed oxide layers were heteroepitaxially grown by coevaporating molecular beam epitaxy. To observe the oxygen release, temperature-programmed desorption was performed. Furthermore, laboratory-based X-ray diffraction measurements were carried out after several annealing steps to investigate the crystal structure rearrangement. The contribution of Ce4+/Ce3+ and Pr4+/Pr3+ redox systems to the oxygen release and lattice rearrangement was clarified by X-ray photoelectron spectroscopy. Finally, Raman spectroscopy was performed to detect structural defects in the oxide lattice (i.e., oxygen vacancies and MO8-c...

Epitaxial oxide thin film layers are of interest for model catalytic studies. We report the growth of Ce 1− x Pr x O 2− δ mixed oxide layers of different stoichiometries ( x =0–1) and oxygen deficiency ( δ >0) on Si(111) by co-evaporating molecular beam epitaxy. The main objective is to identify the crystal phases and to investigate the correlation between compositions and crystal structures. X-ray photoemission spectroscopy was performed to quantify the stoichiometries. An extensive laboratory and synchrotron based X-ray diffraction analysis was carried out to determine the vertical and lateral lattice orientations and the strain status of the layers. The study revealed that single crystalline Ce 1− x Pr x O 2− δ /Si(111) heterostructures can be epitaxially grown on Si(111) for model catalytic studies. In addition to the structure–stoichiometry relationship typical to mixed oxide bulk powders, we identified a hexagonal mixed Ce–Pr oxide thin film phase not yet reported in bulk studies.

Praseodymia films have been exposed to oxygen plasma at room temperature after deposition on Si(111) via molecular beam epitaxy. Different parameters as film thickness, exposure time and flux during plasma treatment have been varied to study their influence on the oxygen plasma oxidation process. The surface near regions have been investigated by means of X-ray photoelectron spectroscopy showing that the plasma treatment transforms the stoichiometry of the films from Pr2O3 to PrO2. Closer inspection of the bulk properties of the films by means of synchrotron radiation based X-ray reflectometry and diffraction confirms this transformation if the films are thicker than some critical thickness of 6 nm. The layer distance of these films is extremely small verifying the completeness of the plasma oxidation process. Thinner films, however, cannot be transformed completely. For all films, less oxidized very thin interlayers are detected by these experimental techniques.

In this work the structural and morphological changes of Ce1−xPrxO2−δ (x = 0.20, 0.35 and 0.75) films grown on Si(111) due to post deposition annealing are investigated by low energy electron diffraction combined with a spot profile analysis. The surface of the oxide films exhibit mosaics with large terraces separated by monoatomic steps. It is shown that the Ce/Pr ratio and post deposition annealing temperature can be used to tune the mosaic spread, terrace size and step height of the grains. The morphological changes are accompanied by a phase transition from a fluorite type lattice to a bixbyite structure. Furthermore, at high PDA temperatures a silicate formation via a polycrystalline intermediate state is observed.

Advanced semiconductor heterostructures are at the very heart of many modern technologies, including aggressively scaled complementary metal oxide semiconductor transistors for high performance computing and laser diodes for low power solid state lighting applications. The control of structural and compositional homogeneity of these semiconductor heterostructures is the key to success to further develop these state-of-the-art technologies. In this article, we report on the lateral distribution of tilt, composition, and strain across step-graded SiGe strain relaxed buffer layers on 300 mm Si(001) wafers treated with and without chemical−mechanical polishing. By using the advanced synchrotron based scanning X-ray diffraction microscopy technique K-Map together with micro-Raman spectroscopyand Atomic Force Microscopy, we are able to establish a partial correlation between real space morphology and structuralproperties of the sample resolved at the micrometer scale. In particular, we demonstrate that the lattice plane bending of thecommonly observed cross-hatch pattern is caused by dislocations. Our results show a strong local correlation between the strain field and composition distribution, indicating that the adatom surface diffusion during growth is driven by strain field fluctuations induced by the underlying dislocation network. Finally, it is revealed that a superficial chemical mechanical polishing of cross-hatched surfaces does not lead to any significant change of tilt, composition, and strain variation compared to that of as-grown complementary metal oxide semiconductor transistors for high performance computing and laser diodes for low power solid state lighting applications. The control of structural and compositional homogeneity of these semiconductor heterostructures is the key to success to further develop these state-of-the-art technologies. In this article, we report on the lateral distribution of tilt, composition, and strain across step-graded SiGe strain relaxed bu ff er layers on 300 mm Si(001) wafers treated with and without chemical − mechanical polishing. By using the advanced synchrotron based scanning X-ray di ff raction microscopy technique K-Map together with micro-Raman spectroscopy and Atomic Force Microscopy, we are able to establish a partial correlation between real space morphology and structural properties of the sample resolved at the micrometer scale. In particular, we demonstrate that the lattice plane bending of the commonly observed cross-hatch pattern is caused by dislocations. Our results show a strong local correlation between the strain fi eld and composition distribution, indicating that the adatom surface di ff usion during growth is driven by strain fi eld fl uctuations induced by the underlying dislocation network. Finally, it is revealed that a super fi cial chemical − mechanical polishing of cross- hatched surfaces does not lead to any significant change of tilt, composition, and strain variation compared to that of as-grown samples

Atomic layer deposited aluminum oxide (ALD-Al2O3) is a dielectric material, which is widely used in organic light emitting diodes in order to prevent their organic layers from humidity related degradation. Unfortunately, there are strong hints that in some cases, ALD-Al2O3 itself is suffering from humidity related degradation. Especially, high temperature and high humidity seem to enhance ALD-Al2O3 degradation strongly. For this reason, the degradation behavior of ALD-Al2O3 films at high temperature and high humidity was investigated in detail and a way to prevent it from degradation was searched. The degradation behavior is analyzed in the first part of this paper. Using infrared absorbance measurements and X-ray diffraction, boehmite (γ-AlOOH) was identified as a degradation product. In the second part of the paper, it is shown that ALD-Al2O3 films can be effectively protected from degradation using a silicon oxide capping. The deposition of very small amounts of silicon in a molecular beam epitaxy syst...

Integration of functional oxides on Si substrates could open a pathway to integrate diverse devices on Si-based technology. Oxygen vacancies (Vo(··)) can strongly affect solid state properties of oxides, including the room temperature ferromagnetism (RTFM) in diluted magnetic oxides. Here, we report a systematical study on the RTFM of oxygen vacancy engineered (by Pr(3+) doping) CeO2 epitaxial thin films on Si substrates. High quality, mixed single crystalline Ce1-xPrxO2-δ (x = 0-1) solid solution films were obtained. The Ce ions in CeO2 with a fluorite structure show a Ce(4+)-dominant valence state in all films. The local crystal structures of the films were analyzed in detail. Pr doping creates both Vo(··) and PrO8-complex defects in CeO2 and their relative concentrations vary with the Pr-doping level. The RTFM properties of the films reveal a strong dependence on the relative Vo(··) concentration. The RTFM in the films initially increases with higher Pr-doping levels due to the increase of the F(+) center (Vo(··) with one occupied electron) concentration and completely disappears when x > 0.2, where the magnetic polaron concentration is considered to decline below the percolation threshold, thus long-range FM order can no longer be established. We thus demonstrate the possibility to directly grow RTFM Pr-doped CeO2 films on Si substrates, which can be an interesting candidate for potential magneto-optic or spintronic device applications.

The local electronic and atomic structure of (111)-oriented, single crystalline mixed Ce1-xPrxO2-delta (x = 0, 0.1 and 0.6) epitaxial thin films on silicon substrates have been investigated in view of engineering redox properties of complex oxide films. Non-destructive X-ray absorption near edge structure reveals that Pr shows only +3 valence and Ce shows only nominal +4 valence in mixed oxides. Extended x-ray absorption fine structure (EXAFS) studies were performed at K edges of Ce and Pr using a specially designed monochromator system for high energy measurements. They demonstrate that the fluorite lattice of ceria (CeO2) is almost not perturbed for x = 0.1 sample, while higher Pr concentration (x = 0.6) not only generates a higher disorder level (thus more disordered oxygen) but also causes a significant reduction of Ce-O interatomic distances. The valence states of the cations were also examined by techniques operating in highly reducing environments: scanning transmission electron microscopy-electron energy loss spectroscopy and X-ray photoemission spectroscopy; in these reducing environments, evidence for the presence of Ce3+ was clearly found for the higher Pr concentration. Thus, the introduction of Pr3+ into CeO2 strongly enhances the oxygen exchange properties of CeO2. This improved oxygen mobility properties of CeO2 are attributed to the lattice disorder induced by Pr mixing in the CeO2 fluorite lattice, as demonstrated by EXAFS measurements. Thus, a comprehensive picture of the modifications of the atomic and electronic structure of Ce1-xPrxO2-delta epitaxial films and their relation is obtained. (C) 2014 AIP Publishing LLC.

Physical chemistry, chemical physics 15(42), 18589-18599 (2013). doi:10.1039/c3cp52688g, The structural changes of a (111) oriented CeO2 film grown on a Si(111) substrate covered with a hex-Pr2O3(0001) interface layer due to post deposition annealing are investigated. X-ray photoelectron spectroscopy measurements revealing the near surface stoichiometry show that the film reduces continuously upon extended heat treatment. The film is not homogeneously reduced since several coexisting crystalline ceria phases are stabilized due to subsequent annealing at different temperatures as revealed by high resolution low energy electron diffraction and X-ray diffraction. The electron diffraction measurements show that after annealing at 660 °C the ι-phase (Ce7O12) is formed at the surface which exhibits a Image ID:c3cp52688g-t1.gif structure. Furthermore, a Image ID:c3cp52688g-t2.gif surface structure with a stoichiometry close to Ce2O3 is stabilized after annealing at 860 °C which cannot be attributed to any bulk phase of ceria stable at room temperature. In addition, it is shown that the fully reduced ceria (Ce2O3) film exhibits a bixbyite structure. Polycrystalline silicate (CeSixOy) and crystalline silicide (CeSi1.67) are formed at 850 °C and detected at the surface after annealing above 900 °C., Published by RSC Publ., Cambridge

The group-IV semiconductor alloy Ge1-x-ySixSny has recently attracted great interest due to its prospective potential for use in optoelectronics, electronics, and photovoltaics. Here, we investigate molecular beam epitaxy grown Ge1-x-ySixSny alloys lattice-matched to Ge with large Si and Sn concentrations of up to 42% and 10%, respectively. The samples were characterized in detail by Rutherford backscattering/channeling spectroscopy for composition and crystal quality, x-ray diffraction for strain determination, and photoluminescence spectroscopy for the assessment of band-gap energies. Moreover, the experimentally extracted material parameters were used to determine the SiSn bowing and to make predictions about the optical transition energy.

The surface morphology of CeO(2)(111) single crystals and silicon supported ceria films is investigated by non-contact atomic force microscopy (NC-AFM) and Kelvin probe force microscopy (KPFM) for various annealing conditions. Annealing bulk samples at 1100 K results in small terraces with rounded ledges and steps with predominantly one O-Ce-O triple layer height while annealing at 1200 K produces well-ordered straight step edges in a hexagonal motif and step bunching. The morphology and topographic details of films are similar, however, films are destroyed upon heating them above 1100 K. KPFM images exhibit uniform terraces on a single crystal surface when the crystal is slowly cooled down, whereas rapid cooling results in a significant inhomogeneity of the surface potential. For films exhibiting large terraces, significant inhomogeneity in the KPFM signal is found even for best possible preparation conditions. Applying X-ray photoelectron spectroscopy (XPS), we find a significant contamination of the bulk ceria sample with fluorine while a possible fluorine contamination of the ceria film is below the XPS detection threshold. Time-of-flight secondary ion mass spectroscopy (TOF-SIMS) reveals an accumulation of fluorine within the first 5 nm below the surface of the bulk sample and a small concentration throughout the crystal.