Bridging the gap between surface physics and photonics.

Use and performance criteria of photonic devices increase in various application areas such as information and communication, lighting, and photovoltaics. In many current and future photonic devices, surfaces of a semiconductor crystal are a weak part causing significant photo-electric losses and malfunctions in applications. These surface challenges, many of which arise from material defects at semiconductor surfaces, include signal attenuation in waveguides, light absorption in light emitting diodes, non-radiative recombination of carriers in solar cells, leakage (dark) current of photodiodes, and light reflection at solar cell interfaces for instance. To reduce harmful surface effects, the optical and electrical passivation of devices has been developed for several decades, especially with the methods of semiconductor technology. Because atomic scale control and knowledge of surface-related phenomena have become relevant to increase the performance of different devices, it might be useful to enhance the bridging of surface physics to photonics. Toward that target, we review some evolving research subjects with open questions and possible solutions, which hopefully provide example connecting points between photonic device passivation and surface physics. One question is related to the properties of the wet chemically cleaned semiconductor surfaces which are typically utilized in device manufacturing processes, but which appear to be different from crystalline surfaces studied in ultrahigh vacuum by physicists. In devices, a defective semiconductor surface often lies at an embedded interface formed by a thin metal or insulator film grown on the semiconductor crystal, which makes the measurements of its atomic and electronic structures difficult. To understand these interface properties, it is essential to combine quantum mechanical simulation methods. This review also covers metal-semiconductor interfaces which are included in most photonic devices to transmit electric carriers to the semiconductor structure. Low-resistive and passivated contacts with an ultrathin tunneling barrier are an emergent solution to control electrical losses in photonic devices.

Atomic-Scale Modification of Oxidation Phenomena on the Ge(100) Surface by Si Alloying.

Properties of Ge oxides are significantly different from those of widely used Si oxides. For example, the instability of GeO x at device junctions causes electronic defect levels that degrade the performance of Ge-containing devices (e.g., transistors and infrared detectors). Therefore, the passivating Si layers have been commonly used at Ge interfaces to reduce the effects of Ge oxide instability and mimic the successful strategy of Si oxidation. To contribute to the atomic-scale knowledge and control of oxidation of such Si-alloyed Ge interfaces (O/Si/Ge), we present a synchrotron radiation core-level study of O/Si/Ge, which is combined with scanning probe microscopy measurements. The oxidation processes and electronic properties of O/Si/Ge(100) are examined as functions of Si amount and oxidation doses. In particular, the incorporation of Si into Ge is shown to cause the strengthening of Ge-O bonds and the increase of incorporated oxygen amount in oxide/Ge junctions, supporting that the method is useful to decrease the defect-level densities.

Oxygen adsorption on (100) surfaces in Fe-Cr alloys.

The adsorption of oxygen on bcc Fe-Cr(100) surfaces with two different alloy concentrations is studied using ab initio density functional calculations. Atomic-scale analysis of oxygen-surface interactions is indispensable for obtaining a comprehensive understanding of macroscopic surface oxidation processes. Up to two chromium atoms are inserted into the first two surface layers. Atomic geometries, energies and electronic properties are investigated. A hollow site is found to be the preferred adsorption site over bridge and on-top sites. Chromium atoms in the surface and subsurface layers are found to significantly affect the adsorption properties of neighbouring iron atoms. Seventy-one different adsorption geometries are studied, and the corresponding adsorption energies are calculated. Estimates for the main diffusion barriers from the hollow adsorption site are given. Whether the change in the oxygen affinity of iron atoms can be related to the chromium-induced charge transfer between the surface atoms is discussed. The possibility to utilize the presented theoretical results in related experimental research and in developing semiclassical potentials for simulating the oxidation of Fe-Cr alloys is addressed.

Decreasing Interface Defect Densities via Silicon Oxide Passivation at Temperatures Below 450 °C.

Low-temperature (LT) passivation methods (<450 °C) for decreasing defect densities in the material combination of silica (SiOx) and silicon (Si) are relevant to develop diverse technologies (e.g., electronics, photonics, medicine), where defects of SiOx/Si cause losses and malfunctions. Many device structures contain the SiOx/Si interface(s), of which defect densities cannot be decreased by the traditional, beneficial high temperature treatment (>700 °C). Therefore, the LT passivation of SiOx/Si has long been a research topic to improve application performance. Here, we demonstrate that an LT (<450 °C) ultrahigh-vacuum (UHV) treatment is a potential method that can be combined with current state-of-the-art processes in a scalable way, to decrease the defect densities at the SiOx/Si interfaces. The studied LT-UHV approach includes a combination of wet chemistry followed by UHV-based heating and preoxidation of silicon surfaces. The controlled oxidation during the LT-UHV treatment is found to provide an until now unreported crystalline Si oxide phase. This crystalline SiOx phase can explain the observed decrease in the defect density by half. Furthermore, the LT-UHV treatment can be applied in a complementary, post-treatment way to ready components to decrease electrical losses. The LT-UHV treatment has been found to decrease the detector leakage current by a factor of 2.

Density Functional Theory description of the order-disorder transformation in Fe-Ni.

The thermodynamic ordering transformation of tetragonal FeNi system is investigated by the Exact Muffin-Tin Orbitals (EMTO) method. The tetragonal distortion of the unit cell is taken into account and the free energy is calculated as a function of long-range order and includes the configurational, vibrational, electronic and magnetic contributions. We find that both configurational and vibrational effects are important and that the vibrational effect lowers the predicted transformation temperature by about 480 K compared to the value obtained merely from the configurational free energy. The predicted temperature is in excellent agreement with the experimental value when all contributions are taken into account. We also perform spin dynamics calculations for the magnetic transition temperature and find it to be in agreement with the experiments. The present research opens new opportunities for quantum-mechanical engineering of the chemical and magnetic ordering in tetrataenite.

Unusual oxidation-induced core-level shifts at the HfO2/InP interface.

X-ray photoelectron spectroscopy (XPS) is one of the most used methods in a diverse field of materials science and engineering. The elemental core-level binding energies (BE) and core-level shifts (CLS) are determined and interpreted in the XPS. Oxidation is commonly considered to increase the BE of the core electrons of metal and semiconductor elements (i.e., positive BE shift due to O bonds), because valence electron charge density moves toward electronegative O atoms in the intuitive charge-transfer model. Here we demonstrate that this BE hypothesis is not generally valid by presenting XPS spectra and a consistent model of atomic processes occurring at HfO2/InP interface including negative In CLSs. It is shown theoretically for abrupt HfO2/InP model structures that there is no correlation between the In CLSs and the number of oxygen neighbors. However, the P CLSs can be estimated using the number of close O neighbors. First native oxide model interfaces for III-V semiconductors are introduced. The results obtained from ab initio calculations and synchrotron XPS measurements emphasize the importance of complementary analyses in various academic and industrial investigations where CLSs are at the heart of advancing knowledge.

Oxidation-Induced Changes in the ALD-Al2O3/InAs(100) Interface and Control of the Changes for Device Processing.

InAs crystals are emerging materials for various devices like radio frequency transistors and infrared sensors. Control of oxidation-induced changes is essential for decreasing amounts of the harmful InAs surface (or interface) defects because it is hard to avoid the energetically favored oxidation of InAs surface parts in device processing. We have characterized atomic-layer-deposition (ALD) grown Al2O3/InAs interfaces, preoxidized differently, with synchrotron hard X-ray photoelectron spectroscopy (HAXPES), low-energy electron diffraction, scanning tunneling microscopy, and time-of-flight elastic recoil detection analysis. The chemical environment and core-level shifts are clarified for well-embedded InAs interfaces (12 nm Al2O3) to avoid, in particular, effects of a significant potential change at the vacuum-solid interface. High-resolution As 3d spectra reveal that the Al2O3/InAs interface, which was sputter-cleaned before ALD, includes +1.0 eV shift, whereas As 3d of the preoxidized (3 × 1)-O interface exhibits a shift of -0.51 eV. The measurements also indicate that an As2O3 type structure is not crucial in controlling defect densities. Regarding In 4d measurements, the sputtered InAs interface includes only a +0.29 eV shift, while the In 4d shift around -0.3 eV is found to be inherent for the crystalline oxidized interfaces. Thus, the negative shifts, which have been usually associated with dangling bonds, are not necessarily an indication of such point defects as previously expected. In contrast, the negative shifts can arise from bonding with O atoms. Therefore, specific care should be directed in determining the bulk-component positions in photoelectron studies. Finally, we present an approach to transfer the InAs oxidation results to a device process of high electron mobility transistors (HEMT) using an As-rich III-V surface and In deposition. The approach is found to decrease a gate leakage current of HEMT without losing the gate controllability.

Crystalline and oxide phases revealed and formed on InSb(111)B.

Oxidation treatment creating a well-ordered crystalline structure has been shown to provide a major improvement for III-V semiconductor/oxide interfaces in electronics. We present this treatment's effects on InSb(111)B surface and its electronic properties with scanning tunneling microscopy and spectroscopy. Possibility to oxidize (111)B surface with parameters similar to the ones used for (100) surface is found, indicating a generality of the crystalline oxidation among different crystal planes, crucial for utilization in nanotechnology. The outcome is strongly dependent on surface conditions and remarkably, the (111) plane can oxidize without changes in surface lattice symmetry, or alternatively, resulting in a complex, semicommensurate quasicrystal-like structure. The findings are of major significance for passivation via oxide termination for nano-structured III-V/oxide devices containing several crystal plane surfaces. As a proof-of-principle, we present a procedure where InSb(111)B surface is cleaned by simple HCl-etching, transferred via air, and post-annealed and oxidized in ultrahigh vacuum.

Variation of magnetic properties of Sr2FeMoO6 due to oxygen vacancies.

Oxygen vacancies can be of utmost importance for improving or deteriorating physical properties of oxide materials. Here, we studied from first-principles the electronic and magnetic properties of oxygen vacancies in the double perovskite Sr2FeMoO6 (SFMO). We show that oxygen vacancies can increase the Curie temperature in SFMO, although the total magnetic moment is reduced at the same time. We found also that the experimentally observed valence change of the Fe ions from 3+ to 2+ in the x-ray magnetic circular dichroism (XMCD) measurements is better explained by oxygen vacancies than by the assumed mixed valence state. The agreement of the calculated x-ray absorption spectra and XMCD results with experimental data is considerably improved by inclusion of oxygen vacancies.

Exchange-Correlation Catastrophe in Cu-Au: A Challenge for Semilocal Density Functional Approximations.

Semilocal density functional approximations occupy the second rung of the Jacob's ladder model and are thus expected to have certain limits to their applicability. A recent study [Y. Zhang, G. Kresse, and C. Wolverton, Phys. Rev. Lett. 112, 075502 (2014)] hypothesizes that the formation energy, being one of the key quantities in alloy theory, would be beyond the grasp of semilocal density functional theory (DFT). Here, we explore the physics of semilocal DFT formation energies and shed light on the connection between the accuracy of the formation energy and the ability of a semilocal approximation to produce accurate lattice constants. We demonstrate that semilocal functionals designed to perform well for alloy constituents can concomitantly solve the problem of alloy formation energies.

Oxidation of the GaAs semiconductor at the Al2O3/GaAs junction.

Atomic-scale understanding and processing of the oxidation of III-V compound-semiconductor surfaces are essential for developing materials for various devices (e.g., transistors, solar cells, and light emitting diodes). The oxidation-induced defect-rich phases at the interfaces of oxide/III-V junctions significantly affect the electrical performance of devices. In this study, a method to control the GaAs oxidation and interfacial defect density at the prototypical Al2O3/GaAs junction grown via atomic layer deposition (ALD) is demonstrated. Namely, pre-oxidation of GaAs(100) with an In-induced c(8 × 2) surface reconstruction, leading to a crystalline c(4 × 2)-O interface oxide before ALD of Al2O3, decreases band-gap defect density at the Al2O3/GaAs interface. Concomitantly, X-ray photoelectron spectroscopy (XPS) from these Al2O3/GaAs interfaces shows that the high oxidation state of Ga (Ga2O3 type) decreases, and the corresponding In2O3 type phase forms when employing the c(4 × 2)-O interface layer. Detailed synchrotron-radiation XPS of the counterpart c(4 × 2)-O oxide of InAs(100) has been utilized to elucidate the atomic structure of the useful c(4 × 2)-O interface layer and its oxidation process. The spectral analysis reveals that three different oxygen sites, five oxidation-induced group-III atomic sites with core-level shifts between -0.2 eV and +1.0 eV, and hardly any oxygen-induced changes at the As sites form during the oxidation. These results, discussed within the current atomic model of the c(4 × 2)-O interface, provide insight into the atomic structures of oxide/III-V interfaces and a way to control the semiconductor oxidation.

The effect of long-range order on the elastic properties of Cu3Au.

Ab initio calculations, based on the exact muffin-tin orbitals method are used to determine the elastic properties of Cu-Au alloys with Au/Cu ratio 1/3. The compositional disorder is treated within the coherent potential approximation. The lattice parameters and single-crystal elastic constants are calculated for different partially ordered structures ranging from the fully ordered L1(2) to the random face centered cubic lattice. It is shown that the theoretical elastic constants follow a clear trend with the degree of chemical order: namely, C(11) and C(12) decrease, whereas C(44) remains nearly constant with increasing disorder. The present results are in line with the experimental findings that the impact of the chemical ordering on the fundamental elastic parameters is close to the resolution of the available experimental and theoretical tools.