This research has been conducted to characterize and validate the resistive heating as a synthesis method for zirconium oxides (ZrO$_2$). A wire of Zr has been oxidized to form a core shell structure, in which the core is the metal wire, and the shell is an oxide layer around 10$μ$m thick. The characterization This research has been conducted to characterize and validate the resistive heating as a synthesis method for zirconium oxides (ZrO$_2$). A wire of Zr has been oxidized to form a core shell structure, in which the core is the metal wire, and the shell is an oxide layer around 10$μ$m thick. The characterization of the samples has been performed by means of Scanning Electron Microscopy (SEM). The chemical composition was analysed by X-ray spectroscopy (EDX). X-ray diffraction (XRD) and Raman spectroscopy have been used to assess crystallinity and crystal structure. Photoluminescence (PL) and cathodoluminescence (CL) measurements have allowed us to study the distribution of defects along the shell, and to confirm the degree of uniformity. The oxygen vacancies, either as isolated defects or forming complexes with impurities, play a determinant role in the luminescent processes. Colour centres, mainly electron centres as F, F$_A$ and F$_{AA}$, give rise to several visible emissions extending from blue to green, with main components around 2eV, 2.4-2.5eV and 2.7eV. The differences between PL and CL are also discussed.
Highly-ordered and spatially-coherent cobalt slanted columnar thin films were deposited by glancing angle deposition onto silicon substrates, and subsequently oxidized by annealing at 475 $^{\circ}$C. Scanning electron microscopy, Raman scattering, generalized ellipsometry, and density functional theory investigations reveal shape-invariant transformation of the slanted nanocolumns from metallic to transparent metal-oxide core-shell structures with properties characteristic of spinel cobalt oxide. We find passivation of Co-SCTFs yielding CoAl$_2$O$_3$ core-shell structures produced by conforma…
Bimetallic nanoparticles are widely studied, for example in catalysis. However, possible restructuring in the environment of use, such as segregation or alloying, may occur. Taken individually, state-of-the-art analytical tools fail to give an overall picture of these transformations. This study combines an ensemble analysis (near-ambient-pressure X-ray photoelectron spectroscopy) with a local analysis (environmental transmission electron microscopy) to provide an in situ description of the restructuring of core--shell nickel-cobalt nanoparticles exposed to cycles of reduction and oxidation. I…
We report the chemical synthesis of Fe-core/Au-shell nanoparticles by a reverse micelle method, and the investigation of their growth mechanisms and oxidation-resistant characteristics. The core-shell structure and the presence of the Fe & Au phases have been confirmed by transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, Mossbauer spectroscopy, and inductively coupled plasma techniques. Additionally, atomic-resolution Z-contrast imaging and electron energy loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) have been used to study d…
Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research, but also technological applications that utilize the subtle change in the physical properties originating from the metal- insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth c…
We show a general two-step method to grow hydroxide and oxide nanocrystals of the iron family elements (Ni, Co, Fe) on graphene with two degrees of oxidation. Drastically different nanocrystal growth behaviors were observed on low-oxidation graphene sheets (GS) and highly oxidized graphite oxide (GO) in hydrothermal reactions. Small particles pre-coated on GS with few oxygen-containing surface groups diffused and recrystallized into single-crystalline nickel hydroxide Ni(OH)2 hexagonal nanoplates or iron oxide Fe2O3 nanorods with well defined morphologies. In contrast, particles pre-coated on …
Submicron core/shell Ti/TiOx photocatalyst is successfully synthesized via single-mode magnetic microwave (SMMW) assisted direct oxidation of planetary ball-milled TiH2. The thickness of TiOx shell including highly concentrated defects such as Ti3+ and/or oxygen vacancies is controllable in the range from 6 to over 18 nm by varying the treatment time in the SMMW assisted reaction. In addition to its quite narrow optical bandgap (1.34-2.69 eV) and efficient visible-light absorption capacity, the submicron Ti/TiOx particle exhibits superior photocatalytic performance towards H2 production from w…
We report the growth of Si nanostructures, either as thin films or nanoparticles, on graphene substrates. The Si nanostructures are shown to be single crystalline, air stable and oxidation resistive, as indicated by the observation of a single crystalline Si Raman mode at around 520 cm-1, a STM image of an ordered surface structure under ambient condition, and a Schottky junction with graphite. Ultra-thin silicon regions exhibit silicene-like behavior, including a Raman mode at around 550 cm-1, a triangular lattice structure in STM that has distinctly different lattice spacing from that of eit…
At the (001) interface between the two band-insulators LaAlO3 and SrTiO3, a high-mobility electron gas may appear, which has been the object of numerous works over the last four years. Its origin is a subject of debate between the interface polarity and unintended doping. Here we use electron energy loss 'spectrum images', recorded in cross-section in a scanning transmission electron microscope, to analyse the Ti3+ ratio, characteristic of extra electrons. We find an interface concentration of Ti3+ that depends on growth conditions.
Large-scale CuO nanowires are commonly synthesized by the thermal oxidation method. However, the growth mechanism remains controversial between diffusion growth mechanism and vapor-solid (VS) growth mechanism. In this study, we investigated the morphology and atomic structure of the CuO nanowires by electron microscopes to clarify the growth mechanism. We found that they were grown with the annealing ambient during the cooling process and there were screw dislocations in the nanowires. These features indicate that the VS growth mechanism is applicable to explain the growth of the CuO nanowires…
A thorough understanding of native oxides is essential for designing semiconductor devices. Here we report a study of the rate and mechanisms of spontaneous oxidation of bulk single crystals of ZrS$_x$Se$_{2-x}$ alloys and MoS$_2$. ZrS$_x$Se$_{2-x}$ alloys oxidize rapidly, and the oxidation rate increases with Se content. Oxidation of basal surfaces is initiated by favorable O$_2$ adsorption and proceeds by a mechanism of Zr-O bond switching, that collapses the van der Waals gaps, and is facilitated by progressive redox transitions of the chalcogen. The rate-limiting process is the formation a…
Zn nanoclusters (NCs) are deposited by Low-energy cluster beam deposition technique. The mechanism of oxidation is studied by analysing their compositional and morphological evolution over a long span of time (three years) due to exposure to ambient atmosphere. It is concluded that the mechanism proceeds in two steps. In the first step, the shell of ZnO forms over Zn NCs rapidly up to certain limiting thickness: with in few days -- depending upon the size -- Zn NCs are converted to Zn-ZnO (core-shell), Zn-void-ZnO, or hollow ZnO type NCs. Bigger than ~15 nm become Zn-ZnO (core-shell) type: amo…
Phenylenediamine (PDA) was chosen as a coordinating, reducing, and capping agent to effectively direct growth and protect against oxidation of Cu nanowires (Cu NWs) in an aqueous solution. PDA was found to reduce Cu (II) to Cu (I) at room temperature, and stabilize the resulting Cu (I) by forming a coordination complex. The presence of a stable Cu (I) complex is the key step in the synthesis of Cu NWs under mild conditions. Different PDA isomers lead to different growth paths of forming Cu NWs. Both pPDA and mPDA-synthesized Cu NWs were covered with a thin layer of polyphenylenediamine and sho…
The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heat…
We propose an innovative, easy-to-implement approach to synthesize large-area singlecrystalline graphene sheets by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain grow…
The internal oxidation of Sn was investigated to understand the oxidation kinetics of monophase CuSn alloys. SnO2 particles were characterized by analytical transmission electron microscopy. The orientation relationship between SnO2 and Cu was determined with a special emphasis on the atomic scale structure of Cu/SnO2 interfaces (misfit dislocations and chemical structure). Habit planes with a pure oxygen plane terminating the SnO2 phase are greatly favored and large misfits promote the growth of plate shaped precipitates.
The localized dielectric breakdown had been considered as the driving force for growth of plasma electrolytic oxide (PEO) coatings for several decades. However, the TEM study here reveals the dielectric breakdown behavior has little contribution for coating thickening. The presented evidences show the nature of PEO coating growth in all three consecutive stages I-III is ionic migration behavior inside the amorphous alumina layer (AAL) at the coating/matrix interface. The evolution of morphological characterizations in the PEO process is attributed to the interfacial reactions of AAL/alkaline (…
Silicon together with its native oxide SiO$_2$ was recognized as an outstanding material system for the semiconductor industry in the 1950s. In state-of-the-art device technology, SiO$_2$ is widely used as an insulator in combination with high-$k$ dielectrics such as HfO$_2$, demanding fabrication of ultra-thin interfacial layers. The classical standard model derived by Deal and Grove accurately describes the oxidation of Si in a progressed stage, however, strongly underestimates growth rates for thin oxide layers. Recent studies report a variety of oxidation mechanisms during the growth of ox…
Titanium is commonly added to nickel superalloys but has a well-documented detrimental effect on oxidation resistance. The present work constitutes the first atomistic-scale quantitative measurements of grain boundary and bulk compositions in the oxide scale of a current generation polycrystalline nickel superalloy performed through atom probe tomography. Titanium was found to be particularly detrimental to oxide scale growth through grain boundary diffusion.
The boosting effect of Cr on the growth of the protective alumina scale on Fe-Al alloys is investigated by x-ray photoelectron spectroscopy. Using low oxygen pressure the surface chemistry of the alloys is monitored starting from the first moments of oxidation. Chromium effect on the Fe-Al surface-bulk exchange is clearly detected by analyzing the measured surface concentrations within the atomic concentration models. Previous ab initio calculations agree well with the present experiments.
We present a detailed atomistic picture of the oxidation mechanism of Co nanoparticles and its impact on magnetism by experimentally following the evolution of the structure, chemical composition, and magnetism of individual, gas-phase grown Co nanoparticles during controlled oxidation. The early stage oxidation occurs in a twostep process characterized by (i) the initial formation of small CoO crystallites randomly distributed across the nanoparticle surface, until their coalescence leads to structural completion of the oxide shell and passivation of the metallic core; (ii) progressive conver…
Passivation mechanisms were investigated on (100)-oriented Fe-18Cr-13Ni surfaces with direct transfer between surface preparation and analysis by X-ray photoelectron spectroscopy and scanning tunneling microscopy and electrochemical characterization. Starting from oxide-free surfaces, pre-oxidation at saturation under ultra-low pressure (ULP) oxygen markedly promotes the oxide film Cr(III) enrichment and hinders/delays subsequent iron oxidation in water-containing environment. Exposure to sulfuric acid at open circuit potential causes preferential dissolution of oxidized iron species. Anodic p…
Tungsten, a plasma-facing material for future fusion reactors, may be exposed to air during abnormal operation or accidents. Only limited information is available on the evolution of related oxide phases. This work addresses the effect of substrate orientation on structural variations of tungsten oxides. Annealing experiments in an argon-oxygen atmosphere have been conducted at T = 400 °C under varying oxygen partial pressure and oxidation time. A combination of EBSD, Raman spectroscopy and confocal microscopy shows preferential oxidation initially on {111} base material planes. The oxide scal…
The major chemical feature of an element is the number of electrons available for forming chemical bonds. A doctrine rooted in the atomic shell model states that the atoms will maintain a complete inner shell while interacting with other atoms. Therefore, group IA elements, for example, are invariably stable in the +1 charge state because the p electrons of their inner shells do not react with other chemical species. This general rule governs our understanding of the structures and reactions of matter and has never been challenged. In this work, we show for the first time that while mixing wit…
The Al-Au binary diffusion couple is a classic example of the system exhibiting Kirkendall voiding during interdiffusion. We demonstrate that this effect, which is a major reason for failures of the wire bonds in microelectronics, can be utilized for producing hollow AlAu2 nanoparticles attached to sapphire substrate. To this end, we produced the core-shell Al-Au nanoparticles by performing a solid state dewetting treatment of Al thin film deposited on sapphire substrate, followed by the deposition of thin Au layer on the top of dewetted sample. Annealing of the core-shell nanoparticles in air…
Crystal growth experiments (micro-pulling down or Czochralski methods, respectively) and DTA/TG measurements with Fe2+ containing olivines (fayalite--forsterite solid solution) and with FeO (wustite) are performed. For both substances the oxygen partial pressure p_O2 of the growth atmosphere had to be adjusted within the stability region of Fe2+ for all temperatures ranging from room temperature to the melting point. The formation of Fe3+ (Fe3O4, Fe2O3) had to be avoided. The adjustment of p_O2 could be obtained by a mixture of argon, carbon dioxide and carbon monoxide. Thermodynamic equilibri…
The growth of a U3O7 oxide layer during the anionic oxidation of UO2 pellets induced very important mechanical stresses due to the crystallographic lattice parameters differences between UO2 and its oxide. These stresses, combined with the chemical processes of oxidation, can lead to the cracking of the system, called chemical fragmentation. We study the crystallographic orientation of the oxide lattice growing at the surface of UO2, pointing the fact that epitaxy relations at interface govern the coexistence of UO2 and U3O7. In this work, several results are given: - Determination of the epit…
The growth of thin oxide coatings on the aluminum substrate in water-based sodium tungstate electrolyte by plasma electrolytic oxidation (PEO) is discussed and experimentally illustrated. The growth is carried out using a distinctive ultra-low duty cycle pulsed direct current (DC) power supply. During the PEO processing elements present in micro-discharges are identified using standard optical emission spectroscopy (OES) technique. The spectral line shape analysis of the first two hydrogen Balmer lines shows the presence of two types of micro-discharges. Obtained coatings are also characterize…
Cuprous oxide (Cu2O) nanowires were grown by a simple, catalyst-free thermal oxidation method starting from a copper foil substrate. Wire growth was performed at different conditions by varying oxygen partial pressure and heating temperature, and produced structural defects such as stacking faults and twin structures of grown nanowires were characterized by transmission electron microscopy. A moderate oxygen partial pressure ~5% with a relatively high temperature at 500 oC is found to be an optimal condition for growing high-quality Cu2O nanowires, while either lowering temperature or enhancin…
Kinetics of silicon dry oxidation are investigated theoretically and experimentally at low temperature in the nanometer range where the limits of the Deal and Grove model becomes critical. Based on a fine control of the oxidation process conditions, experiments allow the investigation of the growth kinetics of nanometric oxide layer. The theoretical model is formulated using a reaction rate approach. In this framework, the oxide thickness is estimated with the evolution of the various species during the reaction. Standard oxidation models and the reaction rate approach are confronted with thes…
It is known that a higher concentration of free carriers leads to a higher oxide growth rate in the thermal oxidation of silicon. However, the role of electrons and holes in oxidation chemistry is not clear. Here, we report real-time second-harmonic-generation data on the oxidation of H-terminated (111)Si that reveal that high concentrations of electrons increase the chemical reactivity of the outer-layer Si-Si back bonds relative to the Si-H up bonds. However, the thicknesses of the natural oxides of all samples stabilize near 1 nm at room temperature, regardless of the chemical kinetics of t…
We use low-energy electron microscopy to investigate how graphene is removed from Ru(0001) and Ir(111) by reaction with oxygen. We find two mechanisms on Ru(0001). At short times, oxygen reacts with carbon monomers on the surrounding Ru surface, decreasing their concentration below the equilibrium value. This undersaturation causes a flux of carbon from graphene to the monomer gas. In this initial mechanism, graphene is etched at a rate that is given precisely by the same non-linear dependence on carbon monomer concentration that governs growth. Thus, during both growth and etching, carbon att…
The oxidation of the Pd(100) surface at oxygen pressures in the 10^-6 to 10^3 mbar range and temperatures up to 1000 K has been studied in-situ by surface x-ray diffraction (SXRD). The results provide direct structural information on the phases present in the surface region and on the kinetics of the oxide formation. Depending on the (T,p) environmental conditions we either observe a thin sqrt(5) x sqrt(5) R27 surface oxide or the growth of a rough, poorly ordered bulk oxide film of PdO predominantly with (001) orientation. By either comparison to the surface phase diagram from first-principle…
We present results on the growth of CdTe-HgTe core-shell nanowires, a realization of a quasi one-dimensional heterostructure of the topological insulator HgTe. The growth is a two step process consisting of the growth of single crystalline zinc blende CdTe nanowires with the vapor-liquid-solid method and the overgrowth of these wires with HgTe such that a closed shell is formed around the CdTe core structure. The CdTe wire growth is monitored by RHEED allowing us to infer information on the crystal properties from the electron diffraction pattern. This information is used to find and control t…
GaAs nanowires and GaAs/Fe3Si core/shell nanowire structures were grown by molecular-beam epitaxy on oxidized Si(111) substrates and characterized by transmission electron microscopy. The surfaces of the original GaAs NWs are completely covered by magnetic Fe3Si exhibiting nanofacets and an enhanced surface roughness compared to the bare GaAs NWs. Shell growth at a substrate temperature of T{S} = 200 °C leads to regular nanofacetted Fe3Si shells. These facets, which lead to thickness inhomogeneities of the shells, consist mainly of well pronounced Fe3Si(111) planes. The crystallographic orient…
We analyze the morphological stability against azimuthal, axial, and general helical perturbations for epitaxial core-shell nanowires in the growth regimes limited by either surface diffusion or evaporation-condensation surface kinetics. For both regimes, we find that geometric parameters (i.e., core radius and shell thickness) play a central role in determining whether the nanowire remains cylindrical or its shell breaks up into epitaxial islands similar to those observed during Stranski-Krastanow growth in thin epilayers. The combination of small cores and rapid growth of the shell emerge as…
Al(0.37)Ga(0.63)As nanowires (NWs) were grown in a molecular beam epitaxy system on GaAs(111)B substrates. Micro-photoluminescence measurements and energy dispersive X-ray spectroscopy indicated a core-shell structure and Al composition gradient along the NW axis, producing a potential minimum for carrier confinement. The core-shell structure formed during the growth as a consequence of the different Al and Ga adatom diffusion lengths.
Multi-AI Agent Framework Reveals the "Oxide Gatekeeper" in Aluminum Nanoparticle Oxidation
Advanced Institute for Materials Research (WPI-AIMR), Tohoku University（东北大学材料科学高等研究所（WPI-AIMR））；School of Chemical Engineering, Dalian University of Technology（大连理工大学化工学院）
The oxidation and corrosion of metals are fundamental problems in materials science and technology that have been studied using a large variety of experimental and computational techniques. Here we review some of the recent studies that have led to significant advances in our atomic-level understanding of copper oxide, one of the most studied and best understood metal oxides. We show that a good atomistic understanding of the physical characteristics of cuprous (Cu$_2$O) and cupric (CuO) oxide and of some key processes of their formation has been obtained. Indeed, the growth of the oxide has b…
Based on first-principles calculations we performed a systematic study of the energetic stability, structural characterization, and electronic properties of the fully oxidized $A_{2}B$, electrenes, with the following combinations, (i) $A$=Ca, Sr, and Ba for $B$=N; (ii) $A$=Sr and Ba for $B$=P; and Y$_{2}$C, and Ba$_{2}$As. We have considered one side oxidation of single layer electrenes $(O/A_{2}B)$, and two side oxidation of bilayer electrenes $(O/(A_{2}B)_{2}/O)$. We show that the hexagonal lattice of the pristine host is no longer the ground state structure in the oxidized systems. Our tota…
Ultrathin cerium oxide films have been deposited on chlorine, gallium, and silver passivated Si(111) by reactive molecular beam epitaxy in a comparative study. The crystallinity of these films has been characterized by x-ray standing waves while the oxidation state of the rare-earth oxide (REOx) films and the chemical interface composition have been revealed by hard x-ray photoelectron spectroscopy. The use of Cl as passivating agent results in the epitaxial growth of highly crystalline REOx films with the RE metal in the 3+ oxidation state while effectively suppressing silicate and silicon ox…
Nanolithography based on local oxidation with a scanning force microscope has been performed on an undoped GaAs wafer and a Ga[Al]As heterostructure with an undoped GaAs cap layer and a shallow two-dimensional electron gas. The oxide growth and the resulting electronic properties of the patterned structures are compared for constant and modulated voltage applied to the conductive tip of the scanning force microscope. All the lithography has been performed in non-contact mode. Modulating the applied voltage enhances the aspect ratio of the oxide lines, which significantly strengthens the insula…
By means of ab-initio calculations, we have investigated the chemisorption paroperties of ethanol onto segregating binary nanoalloys. We select nanostructures with icosahedral shape of 55 atoms with a Pt outermost layer over a M core with M=Ag,Pd,Ni. With respect to nanofilms with equivalent composition, there is an increse of the ethanol binding energy. This is not merely due to observed shortening of the Pt-O distance but depends on the nanoparticle distortion after ethanol adsorption. This geometrical distortion within the nanoparticle can be interpreted as a radial breathing, which is sens…
One-dimensional (1D) nanostructures - nanowires (NWs) - exhibit promising properties for integration in different types of functional devices. Their properties can be enhanced even further or tuned for a specific application by combining different promising materials, such as layered van der Waals materials and conventional semiconductors, into 1D-1D core-shell heterostructures. In this work, we demonstrated growth of GaN-MoS2 and GaN-WS2 core-shell NWs via two different methods: (1) two-step process of sputter-deposition of a sacrificial transition metal oxide coating on GaN NWs followed by s…
A cluster deposition method was used to produce films of loosely aggregated nanoclusters (NC) of Fe core-Fe3O4 shell or fully oxidized Fe3O4. Films of these NC on Si(100) or MgO(100)/Fe3O4(100) were irradiated to 10^16 Si2+/cm2 near room temperature using an ion accelerator. Ion irradiation creates structural change in the NC film with corresponding chemical and magnetic changes which depend on the initial oxidation state of the cluster. Films were characterized using magnetometry (hysteresis, first order reversal curves), microscopy (transmission electron, helium ion), and x-ray diffraction. …
We report the growth of an unstable shell-like gold structure around dihexagonal pyramidal CdSe nanocrystals in organic solution and the structural transformation to spherical domains by two means: i) electron beam irradiation (in situ) and (ii) addition of a strong reducing agent during synthesis. By varying the conditions of gold deposition, such as ligands present or the geometry of the CdSe nanocrystals, we were able to tune the gold domain size between 1.4 nm to 3.9 nm and gain important information on the role of surface chemistry in hetero nanoparticle synthesis and seed reactivity, bot…
Coupling at the interface of core/shell magnetic nanoparticles is known to be responsible for the exchange bias (EB) and the relative sizes of core and shell components are supposed to influence the associated phenomenology. In this work, we have prepared core/shell structured nanoparticles with the total averaged diameter around $\sim$ 27 nm and a wide range of shell thicknesses through the controlled oxidation of Co nanoparticles well dispersed in an amorphous silica host. Structural characterizations give compelling evidence of the formation of Co$_3$O$_4$ crystallite phase at the shells su…
We present a simple method to prove the presence of an organic shell around silver nanoparticles. This method is based on the comparison between optical extinction measurements of isolated nanoparticles and Mie calculations predicting the expected wavelength of the Localized Surface Plasmon Resonance of the nanoparticles with and without the presence of an organic layer. This method was applied to silver nanoparticles which seemed to be well protected from oxidation. Further experimental characterization via Surface Enhanced Raman Spectroscopy (SERS) measurements allowed to identify this prote…
Growth of catalyst-free AlxGa1-xN (0.15<x<0.50)/GaN nanowires by plasma assisted molecular beam epitaxy is thoroughly structural and chemical analyzed by using transmission electron microscopy related techniques. We found that well-defined and defect-free core-shell structures are spontaneously formed during the wire growth. An Al-rich shell with significantly higher Al composition pseudomorphically encapsulates a Ga-rich AlxGa1-xN core with an atomically-abrupt hetero-interface. Nevertheless, the energy dispersive X-Ray spectroscopy reveals a complex chemical composition gradient along the wi…
We have conducted a detailed thin film growth structure of oxygen engineered monoclinic HfO$_{2\pm x}$ grown by reactive molecular beam epitaxy (MBE). The oxidation conditions induce a switching between ($\bar{1}11$) and (002) texture of hafnium oxide. The band gap of oxygen deficient hafnia decreases with increasing amount of oxygen vacancies by more than 1 eV. For high oxygen vacancy concentrations, defect bands form inside the band gap that induce optical transitions and $p$-type conductivity. The resistivity changes by several orders of magnitude as a function of oxidation conditions. Oxyg…
