Chasing H- in Rare-earth Metal Oxyhydride Thin Films

Rare-earth metal oxyhydride thin films show a photochromic effect, where their transparency decreases (reversibly) with exposure to light with energy greater than its optical band gap. The precise underlying mechanism behind this effect is unknown, but is investigated in this thesis by using techniques such as muon spin relaxation, or materials science methods (aliovalent doping, changing the RE-cation, or altering the O:H ratio of the film). Rare-earth metal oxyhydrides have also been reported as hydride-ion conductors in their bulk form (powder pellets). Since some theories about photochromism involve diffusion, there was a suspicion that these two properties are related. Herein, ion mobility is addressed by electrochemical impedance spectroscopy, along with the other aforementioned methods. In summary, this thesis asserts that (1) photochromism does not involve long-range ion mobility and (2) some of the thin films made here are dominated by electronic rather than ionic mobility. An alternative idea for photochromism is given, where neutral hydrogen (H0) is formed alongside the reduced RE-cation (RE2+), and no mobility is required to prolong this darkened state. The local composition of the film under illumination, therefore, may be a H-deficient phase which is optically dark and highly conductive.ChemE/Materials for Energy Conversion & Storag

Influence of Crystal Structure, Encapsulation, and Annealing on Photochromism in Nd Oxyhydride Thin Films

Thin films of rare earth metal oxyhydrides show a photochromic effect, the precise mechanism of which is yet unknown. Here, we made thin films of NdH3-2xOx and show that we can change the band gap, crystal structure, and photochromic contrast by tuning the composition (O2-:H-) via the sputtering deposition pressure. To protect these films from rapid oxidation, we add a thin ALD coating of Al2O3, which increases the lifetime of the films from 1 day to several months. Encapsulation of the films also influences photochromic bleaching, changing the time dependency from first-order kinetics. As well, the partial annealing which occurs during the ALD process results in a dramatically slower bleaching speed, revealing the importance of defects for the reversibility (bleaching speed) of photochromism. ChemE/Materials for Energy Conversion & StorageInstrumenten groepChemE/O&O groepChemE/Chemical Engineerin

Influence of Cation (RE = Sc, Y, Gd) and O/H Anion Ratio on the Photochromic Properties of REO_xH_3-2x Thin Films

Rare-earth oxyhydride REOxH3-2x thin films prepared by air-oxidation of reactively sputtered REH2 dihydrides show a color-neutral, reversible photochromic effect at ambient conditions. The present work shows that the O/H anion ratio, as well as the choice of the cation, allow to largely tune the extent of the optical change and its speed. The bleaching time, in particular, can be reduced by an order of magnitude by increasing the O/H ratio, indirectly defined by the deposition pressure of the parent REH2. The influence of the cation (RE = Sc, Y, Gd) under comparable deposition conditions is discussed. Our data suggest that REs of a larger ionic radius form oxyhydrides with a larger optical contrast and faster bleaching speed, hinting to a dependency of the photochromic mechanism on the anion site-hopping.ChemE/Materials for Energy Conversion & StorageRST/Fundamental Aspects of Materials and EnergyChemE/Chemical Engineerin

Perspective on the photochromic and photoconductive properties of Rare-Earth Oxyhydride thin films

Rare-Earth oxyhydrides (REH3-2xOx) are characterized by photodarkening when illuminated by photons having an energy exceeding that of the band gap. We propose that the film is segregated in hydrogen rich and hydrogen poor areas. Upon illumination, the excited electrons reduce the three-valent cations inducing an insulator to metal transition in the hydrogen rich entities. These small metallic oxyhydride clusters are responsible for the enhanced optical absorption. In the surrounding semiconductor matrix the photoexcitation induces a transition from p to n-type conductivity. This persistent photoconductivity is due to trapping of the holes by hydride ions. As a result, the Fermi level rises above the conduction band inducing a Burstein-Moss effect and a large increase in the conductivity.ChemE/Materials for Energy Conversion and StorageRST/Fundamental Aspects of Materials and Energ

Structural properties and anion dynamics of yttrium dihydride and photochromic oxyhydride thin films examined by in situ μ+SR

Thin films of rare-earth metal oxyhydrides, such as yttrium oxyhydrides (YH3-2xOx), show a photochromic effect where the transparency of the films decreases reversibly upon exposure to UV light. However, the exact mechanism behind this effect is unknown. In this paper, we describe the behavior of YH3-2xOx thin films, with different O2-:H- ratios, under dark and illuminated conditions using in situ muon spin relaxation (μ+SR), and compare that to an oxygen-free reference compound, yttrium dihydride (YH2-δ). The muon acts as a local magnetic probe in our compounds, giving information related to electronic, structural, and photochromic properties. Although YH2-δ is the parent compound to YH3-2xOx, the muon behavior in these two materials is different - the muon electrostatically interacts primarily with H- (dihydride) or O2- (oxyhydride) - leading to the use of different theoretical models. For YH2-δ, we observed the formation of an entangled H-μ complex and the onset of Mu+ diffusion and H- rearrangement above 150 K (EA,Γ=67±13meV). For the oxyhydrides, we adopted a transition state model, where Mu0 formation and gradual Mu+ recovery take place, accompanied by the formation of a Mu+-O2- complex and a polaron at the Y cation. The activation energy (EA,dia) associated with Mu+ recovery is dependent on lattice relaxation and is lower for thin films of higher H content (EA,dia=29-45meV). In situ illumination further reduces this energy barrier for all measured oxyhydrides, suggesting that the photochromic effect involves a reversible structural rearrangement during photodarkening. RST/Fundamental Aspects of Materials and EnergyChemE/Materials for Energy Conversion & StorageChemE/O&O groepChemE/Chemical Engineerin

Exploring Multi-Anion Chemistry in Yttrium Oxyhydrides: Solid-State NMR Studies and DFT Calculations

Rare earth oxyhydrides REOxH(3-2x), with RE = Y, Sc, or Gd and a cationic FCC lattice, are reversibly photochromic in nature. It is known that structural details and anion (O2-:H-) composition dictate the efficiency of the photochromic behavior. The mechanism behind the photochromism is, however, not yet understood. In this study, we use 1H, 2H, 17O, and 89Y solid-state NMR spectroscopy and density functional theory (DFT) calculations to study the various yttrium, hydrogen, and oxygen local environments, anion oxidation states, and hydride ion dynamics. DFT models of YOxH(3-2x) with both anion-ordered and anion-disordered sublattices are constructed for a range of compositions and show a good correlation with the experimental NMR parameters. Two-dimensional 17O-1H and 89Y-1H NMR correlation experiments reveal heterogeneities in the samples, which appear to consist of hydride-rich (x ≈ 0.25) and hydride-poor domains (x ≈ 1) rather than a single composition with homogeneous anion mixing. The compositional variation (as indicated by the different x values in YOxH(3-2x)) is determined by comparing static 1H NMR line widths with calculated 1H-1H dipolar couplings of yttrium oxyhydride models. The 1D 17O MAS spectrum demonstrates the presence of a small percentage of hydroxide (OH-) ions. DFT modeling indicates a reaction between the protons of hydroxides and hydrides to form molecular hydrogen (H+ + H- → H2). 1H MAS NMR indicates the presence of a mobile component that, based on this finding, is attributed to trapped molecular H2 in the lattice.ChemE/Materials for Energy Conversion and StorageRST/Fundamental Aspects of Materials and EnergyChemE/Chemical Engineerin

Energy, metastability, and optical properties of anion-disordered R Ox H3-2x (R= Y, La) oxyhydrides: A computational study

In this paper, we investigate by ab initio DFT how the O:H ratio influences the formation and lattice energy, metastability, and optical properties of Y and La anion-disordered ROxH3-2x oxyhydrides. To achieve this, a set of special quasirandom structures (SQS) is introduced to model anion-disorder along the whole RH3-R2O3 composition line. A comparison with an extensive set of anion-ordered polymorphs of the same composition shows the comparable energy of the anion-disordered phase, which, in particular, in the H-rich composition interval showed the lowest relative energy. In turn, the metastability of the anion-disordered phase depends on the cation size (Y versus La), which determines the maximum H content above which the CaF2-type structure itself becomes unstable. To overcome the accuracy limitations of classical DFT, the modified Becke-Johnson (mBJ) scheme is employed in the study of the electronic properties. We show that major differences occur between H-rich and O-rich R oxyhydrides, as the octahedral H- present for x<1 form electronic states at the top of the valence band, which reduce the energy band gap and dominate the electronic transitions at lower energies, thus increasing the refractive index of the material in the VIS-nIR spectral range. Comparing the DFT results to experimental data on photochromic Y oxyhydride films reinforces the hypothesis of anion-disorder in the H-rich films (x<1), while it hints towards some degree of anion ordering in the O-rich ones (x>1). Our paper exemplifies a strategy to calculate ab initio the electronic/optical properties of a wide range of materials with occupational disorder.ChemE/Materials for Energy Conversion & StorageFluid MechanicsRST/Fundamental Aspects of Materials and EnergyChemE/Chemical Engineerin

Photochromic YO_xH_y thin films examined by in situ positron annihilation spectroscopy

Doppler broadening positron annihilation spectroscopy depth profiles were collected on photochromic YOxHy thin films. In situ UV illumination of photochromic semiconductor YOxHy films leads to an increase in S-parameter and a large reduction in W-parameter, possibly caused by a change in the charge state of vacancies or the growth of hydrogen-rich metallic Y(Ox)Hy clusters, albeit that vacancy formation or changes in positronium formation during illumination might also play a role. Intriguingly, both the S- and W-parameters increase during thermal bleaching, indicating that another process takes place. The Doppler parameters do not return to their initial values after complete thermal bleaching, suggesting that persistent local rearrangements of vacancies and possibly hydride ions have occurred during the full photodarkening-thermal bleaching cycle. Positron annihilation lifetime spectroscopy shows that a small fraction of positronium is formed in as-deposited YOxHy films, indicating that the films contain some nanopores.RST/Fundamental Aspects of Materials and EnergyChemE/Materials for Energy Conversion & StorageRST/Neutron and Positron Methods in MaterialsChemE/Chemical Engineerin

Formation of vacancies and metallic-like domains in photochromic rare-earth oxyhydride thin films studied by in-situ illumination positron annihilation spectroscopy

Rare-earth (RE) oxyhydride thin films show a color-neutral, reversible photochromic effect at ambient conditions. The origin of the photochromism is the topic of current investigations. Here, we investigated the lattice defects, electronic structure, and crystal structure of photochromic YHxOy and GdHxOy thin films deposited by magnetron sputtering using positron annihilation techniques and X-ray diffraction, in comparison with Y, YH∼1.9, Y2O3, Gd, GdH∼1.8, and Gd2O3 films. Positron annihilation lifetime spectroscopy (PALS) reveals the presence of cation monovacancies in the as-deposited Y and YH∼1.9 films at concentrations of ∼10-5 per cation. In addition, vacancy clusters and nanopores are found in the as-prepared YHxOy and Y2O3 films. Doppler broadening positron annihilation spectroscopy (DB-PAS) of the Y- A nd Gd-based films reflects the transition from a metallic to an insulating nature of the RE metal, metal hydride, semiconducting oxyhydride and insulating oxide films. In-situ illumination DB-PAS shows the irreversible formation predominantly of di-vacancies, as PALS showed that cation mono-vacancies are already abundantly present in the as-prepared films. The formation of di-vacancies supports conjectures that H-(and/or O2-) ions become mobile upon illumination, as these will leave anion vacancies behind, some of which may subsequently cluster with cation vacancies present. In addition, in RE oxyhydride films, partially reversible shifts in the Doppler parameters are observed that correlate with the photochromic effect and point to the formation of metallic domains in the semiconducting films. Two processes are discussed that may explain the formation of these metallic domains and the changes in optical properties associated with the photochromic effect. The first process considers the reversible formation of metallic nanodomains with reduced O: H composition by transport of light-induced mobile hydrogen and local oxygen displacements. The second process considers metallic nanodomains resulting from the trapping of photoexcited electrons in an eg orbital at the yttrium ions surrounding positively charged hydrogen vacancies that are formed by light-induced removal of hydrogen atoms from octahedral sites. When a sufficiently large concentration, on the order of ∼10%, is reached in a certain domain of the film, band formation of the eg electrons may occur, leading to an Anderson-Mott insulator-metal transition like the case of yttrium trihydride in these domains.RST/Fundamental Aspects of Materials and EnergyChemE/Materials for Energy Conversion & StorageApplied SciencesRST/Neutron and Positron Methods in MaterialsChemE/Chemical Engineerin

Aliovalent Calcium Doping of Yttrium Oxyhydride Thin Films and Implications for Photochromism

To develop an understanding of the photochromic effect in rare-earth metal oxyhydride thin films (REH3-2xOx, here RE = Y), we explore the aliovalent doping of the RE cation. We prepared Ca-doped yttrium oxyhydride thin films ((CazY1-z)HxOy) by reactive magnetron cosputtering with Ca doping concentrations between 0 and 36 at. %. All of the films are semiconductors with a constant optical band gap for Ca content below 15%, while the band gap expands for compositions above 15%. Ca doping affects the photochromic properties, resulting in (1) a lower photochromic contrast, likely due to a lower H- concentration, and (2) a faster bleaching speed, caused by a higher pre-exponential factor. Overall, these results point to the importance of the H- concentration for the formation of a "darkened"phase and the local rearrangement of these H- for the kinetics of the process. ChemE/Materials for Energy Conversion & StorageQN/Kavli Nanolab DelftChemE/O&O groepRST/Fundamental Aspects of Materials and EnergyInstrumenten groepRST/Storage of Electrochemical EnergyChemE/Chemical Engineerin