Reactive laser interference patterning on titanium and zinc in high pressure CO2

Direct laser interference patterning (DLIP) is a versatile technique for surface patterning that enables formation of micro-nano sized periodic structures on top of the target material. In this study, DLIP in high pressure, supercritical and liquid CO2 by 4-beam DLIP was used to pattern titanium and zinc targets. Field emission scanning electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy was used to characterize the patterned surfaces. Field emission SEM analysis showed presence of ordered uniform donut ring pattern with hollow centers for both titanium and zinc with a period slightly under 3 µm while topographical images from atomic force microscopy revealed donut rings protruding outwards typically around 200 nm from target surface and consisted of a crevice at the center with a depth typically around 300 nm and 250 nm for titanium and zinc target, respectively. Based on X-ray photoelectron spectroscopic analysis, this is the first study to report formation of TiO2, TiC, ZnCO3, and zinc hydroxy carbonate on the pattern by DLIP in supercritical and liquid CO2 for titanium and zinc targets. Pressurized CO2 is demonstrated as a promising environment with mirror-based DLIP system for reactive patterning. Due to the superior transport properties and solvent power of supercritical CO2, the current study opens possibilities for reactive patterning in environments that may not have been previously possible.publishedVersionPeer reviewe

Grain orientation dependent Nb-Ti microalloying mediated surface segregation on ferritic stainless steel

Surface segregation and oxide formation anisotropy on Ti-Nb stabilized ferritic stainless steel (EN 1.4521) were studied by XPS and Electron Backscatter Diffraction. Competitive surface segregation of Si, Nb and Ti was initiated at ∼550. °C, and segregation was favored to the open surface sites of 〈111〉 oriented grains. Furthermore, the surface segregation of Cr was strongly limited at the locations of stable Ti(CN)- and (NbTi)C-type precipitates. Consequently, the oxidation resistance of stainless steels can be enhanced cost-efficiently, without alloy additions, by optimizing the microstructure to facilitate the fast and uniform growth of protective oxide scale.acceptedVersionPeer reviewe

High-Power 1180-nm GaInNAs DBR Laser Diodes

We report high-power 1180-nm GaInNAs distributed Bragg reflector laser diodes with and without a tapered amplifying section. The untapered and tapered components reached room temperature output powers of 655 mW and 4.04 W, respectively. The diodes exhibited narrow linewidth emission with side-mode suppression ratios in the range of 50 dB for a broad range of operating current, extending up to 2 A for the untapered component and 10 A for the tapered component. The high output power is rendered possible by the use of a high quality GaInNAs-based quantum well gain region, which allows for lower strain and better carrier confinement compared with traditional GaInAs quantum wells. The development opens new opportunities for the power scaling of frequency-doubled lasers with emission at yellow–orange wavelengths.publishedVersionPeer reviewe

Low-Temperature Route to Direct Amorphous to Rutile Crystallization of TiO2Thin Films Grown by Atomic Layer Deposition

The physicochemical properties of titanium dioxide (TiO2) depend strongly on the crystal structure. Compared to anatase, rutile TiO2 has a smaller bandgap, a higher dielectric constant, and a higher refractive index, which are desired properties for TiO2 thin films in many photonic applications. Unfortunately, the fabrication of rutile thin films usually requires temperatures that are too high (>400 °C, often even 600-800 °C) for applications involving, e.g., temperature-sensitive substrate materials. Here, we demonstrate atomic layer deposition (ALD)-based fabrication of anatase and rutile TiO2 thin films mediated by precursor traces and oxide defects, which are controlled by the ALD growth temperature when using tetrakis(dimethylamido)titanium(IV) (TDMAT) and water as precursors. Nitrogen traces within amorphous titania grown at 100 °C inhibit the crystal nucleation until 375 °C and stabilize the anatase phase. In contrast, a higher growth temperature (200 °C) leads to a low nitrogen concentration, a high degree of oxide defects, and high mass density facilitating direct amorphous to rutile crystal nucleation at an exceptionally low post deposition annealing (PDA) temperature of 250 °C. The mixed-phase (rutile-brookite) TiO2 thin film with rutile as the primary phase forms upon the PDA at 250-500 °C that allows utilization in broad range of TiO2 thin film applications.publishedVersionPeer reviewe

Charge carrier dynamics in tantalum oxide overlayered and tantalum doped hematite photoanodes

We employ atomic layer deposition to prepare 50 nm thick hematite photoanodes followed by passivating them with a 0.5 nm thick Ta2O5-overlayer and compare them with samples uniformly doped with the same amount of tantalum. We observe a three-fold improvement in photocurrent with the same onset voltage using Ta-overlayer hematite photoanodes, while electrochemical impedance spectroscopy under visible light irradiation shows a decreased amount of surface states under water splitting conditions. The Tadoped samples have an even higher increase in photocurrent along with a 0.15 V cathodic shift in the onset voltage and decreased resistivity. However, the surface state capacitance for the Ta-doped sample is twice that of the reference photoanode, which implies a larger amount of surface hole accumulation. We further utilize transient absorption spectroscopy in the sub-millisecond to second timescale under operating conditions to show that electron trapping in both Ta2O5-passivated and Ta-doped samples is markedly reduced. Ultrafast transient absorption spectroscopy in the sub-picosecond to nanosecond timescale shows faster charge carrier dynamics and reduced recombination in the Ta-doped hematite photoanode resulting in the increased photoelectrochemical performance when compared with the Ta2O5-overlayer sample. Our results show that passivation does not affect the poor charge carrier dynamics intrinsic to hematite based photoanodes. The Ta-doping strategy results in more efficient electron extraction, solving the electron trapping issue and leading to increased performance over the surface passivation strategy.Peer reviewe

Pinhole-resistant nanocrystalline rutile TiO2 photoelectrode coatings

Atomic layer deposited (ALD) TiO2 thin films have a wide range of applications in photonics which are, however, limited by the chemical instability of the amorphous as-deposited TiO2. Post-deposition annealing is required for improving the performance by inducing phase transitions and oxide defects. ALD precursor traces remaining in the TiO2 film affect the thermally-induced processes but the understanding of the effect of growth temperature on precursor traces in the film as well as on the thermally-induced processes is weak. In this study 30 nm ALD TiO2 was grown on Si wafer from tetrakis(dimethylamido)titanium and water at 100–200 °C. TiO2 was subsequently annealed in vacuum at 200–500 °C. Increasing the growth temperature decreased the amount of N bearing precursor traces and thus makes the TiO2 more easily reducible. The reduction takes place simultaneously with the crystallization and formation of O1− defects. Vacuum annealing of TiO2 with less than 0.3 at% of N results in nanocrystalline rutile whereas samples with more N containing traces crystallized as microcrystalline anatase. Nanocrystalline rutile TiO2 was chemically stable and resistant to the dissolution at the grain boundaries under alkaline conditions making it a suitable material for protective photoelectrode coatings used in artificial photosynthesis.publishedVersionPeer reviewe

Functionalization of TiO2 inverse opal structure with atomic layer deposition grown Cu for photocatalytic and antibacterial applications

TiO2 inverse opal (IO) structure surfaces were functionalized with a sub-monolayer amount of Cu by atomic layer deposition (ALD) and tested for photocatalytic and antimicrobial applications. Decomposition of acetylene (C2H2) into CO2 and reduction of CO2 into CH4 were tested in the gas phase and photodegradation of methylene blue (MB) was tested in the liquid phase. Antimicrobial activity was tested against Gram-positive Staphylococcus aureus (S. aureus) bacteria. ALD Cu without any post-deposition heat treatment (HT) decreased the photo degradation rate of both C2H2 and MB but improved the activity towards CO2 reduction. ALD Cu increased MB photodegradation rate and antimicrobial activity only after HT at 550 C, which was linked to the improved chemical stability Cu after the HT. The same HT decreased the activity towards CO2 reduction and decomposition of C2H2. The HT induced desorption of loosely bound ALD Cu+/2+ from the TiO2 IO surface and the remaining Cu+/2+ was reduced to Cu+. The photocatalytic and antimicrobial activity of TiO2 IO can be tailored by the addition of a sub-monolayer amounts of Cu with performance depending on the targeted reaction

Design aspects of all atomic layer deposited TiO2–Fe2O3 scaffold-absorber photoanodes for water splitting

Iron and titanium oxides have attracted substantial attention in photoelectrochemical water splitting applications. However, both materials suffer from intrinsic limitations that constrain the final device performance. In order to overcome the limitations of the two materials alone, their combination has been proposed as a solution to the problems. Here we report on the fabrication of an atomic layer deposited (ALD) Fe2O3 coating on porous ALD-TiO2. Our results show that successful implementation requires complete mixing of the TiO2 and Fe2O3 layers via annealing resulting in the formation of a photoactive iron titanium oxide on the surface. Moreover, we found that incomplete mixing leads to crystallization of Fe2O3 to hematite that is detrimental to the photoelectrochemical performance. IPCE and transient photocurrent measurements performed using UV and visible light excitation confirmed that the iron titanium oxide extends the photocurrent generation to the visible range. These measurements were complemented by transient absorption spectroscopy (TAS), which revealed a new band absent in pristine hematite or anatase TiO2 that we assign to charge transfer within the structure. Taken together, these results provide design guidelines to be considered when aiming to combine TiO2 and Fe2O3 for photoelectrochemical applications.Peer reviewe

Visible to near-infrared broadband fluorescence from Ce-doped silica fiber

We investigate the fluorescence characteristics of a purely Ce-doped silica fiber and demonstrate broad-bandwidth fluorescence across the visible and near-infrared. The Ce-doped fiber is fabricated using standard modified chemical vapor deposition technology. Trace metal analysis by inductively coupled plasma mass spectrometry confirmed the purity of Ce-doping. The Ce valence state of 3+ was revealed by X-ray photoelectron spectroscopy. The optimum pump wavelength for the broadest luminescence from a fiber is scanned between 405 nm to 440 nm wavelength of diode lasers operating under continuous-wave regime. The strongest pump absorption is observed at the wavelength of 405 nm. Variation of pump power and fiber length results in the demonstration of broad-bandwidth fluorescence with spectral widths up to 301 nm (at -10 dB). The measured fluorescence spectra cover the wavelength range from ∼458 nm to ∼819 nm with spectral power densities of up to 2.4 nW/nm

Enhancing the Microstructure of Perovskite-Inspired Cu-Ag-Bi-I Absorber for Efficient Indoor Photovoltaics

Lead-free perovskite-inspired materials (PIMs) are gaining attention in optoelectronics due to their low toxicity and inherent air stability. Their wide bandgaps (≈2 eV) make them ideal for indoor light harvesting. However, the investigation of PIMs for indoor photovoltaics (IPVs) is still in its infancy. Herein, the IPV potential of a quaternary PIM, Cu2AgBiI6 (CABI), is demonstrated upon controlling the film crystallization dynamics via additive engineering. The addition of 1.5 vol% hydroiodic acid (HI) leads to films with improved surface coverage and large crystalline domains. The morphologically-enhanced CABI+HI absorber leads to photovoltaic cells with a power conversion efficiency of 1.3% under 1 sun illumination-the highest efficiency ever reported for CABI cells and of 4.7% under indoor white light-emitting diode lighting-that is, within the same range of commercial IPVs. This work highlights the great potential of CABI for IPVs and paves the way for future performance improvements through effective passivation strategies.</p