Grazing Incidence X-ray Diffraction Research Articles

Direct Laser Writing Crystal Polymorphs of Organic Semiconductors for Phase Change Electronics.

The many diverse polymorphic behaviors observed in organic electronic materials offer opportunities to modulate electronic properties through reversibly switching crystal structures. Here, we access the prolific polymorphism observed in two-dimensional quinoidal terthiophene via laser writing to locally heat and direct the phase transitions. We access a metastable polymorph IV through rapid cooling and observe distinct symmetry as well as packing through grazing incidence X-ray diffraction (GIXD). Using our open-source PolyChemPrint patterning platform, we direct laser heating to initiate the IV-I transition, switching the conductance by >2 orders of magnitude. This is confirmed via a combination of GIXD and Raman spectroscopy. Finally, we demonstrate switching of transistor devices as well as discrete tuning of conductance via laser writing.

Influence of topography on nano-mechanical properties of cylindrical magnetron sputtered TiN films

Numerous studies on Nano-mechanical behavior of the thin films explained primarily in terms of their film morphology and particle size rather than film topography. Therefore, the current study investigates the effect of film topography on the nano-mechanical characteristics of the film. Ti/TiN multilayer thin films were deposited at varying deposition pressures by using an indigenously developed Cylindrical Magnetron Sputtering (CMS) unit. Surface crystallographic information is characterized by synchrotron-based Grazing Incidence XRD analysis. Film growth follows self-assembled nano hill architecture as revealed by AFM and in situ Scanning Probe Microscopy images. The tribo-mechanical properties of the film is dependent on the height and spacing of its self-assembled structure, which experiences either crushing or buckling under the indenter load, thereby affecting film characteristics. Film deposited at moderate pressure exhibits superior wear behavior, attributed to the interplay between Plasticity Index (PI) and Depth Recovery Ratio (DRR). The study primarily focused on film growth phenomena by using cylindrical targets and their influence on nanomechanical properties of the film.

Fabricating Cu2Zn(SnxGe1-x)Se4 thin-film solar cells with back surface Ge grading by magnetron sputtering

In this paper, an approach of forming a band gap gradient by depositing a layer of Ge between the Mo layers by magnetron sputtering is proposed. The diffusion depth of the Ge into Cu2ZnSnSe4 (CZTSe) thin film can be effectively controlled by the Mo transition layer, resulting in the formation of Cu2Zn(SnxGe1-x)Se4 (CZTGSe) thin film with a band gap grading along the back surface. To validate the formation of the Ge gradient in the absorber, energy dispersive spectrometer line scanning and grazing incidence X-ray diffraction were performed. Furthermore, the impact of Ge layer on the morphologies of CZTSe was assessed using scanning electron microscopy. As a result, the introduced Ge layer formed a Ge grading along the back surface and improved the crystal quality of the absorber. Compared to CZTSe solar cells, the power conversion efficiency (PCE) of CZTGSe solar cells with a Ge gradient improved from 5.79 % to 9.28 %.

Deposition pressure-controlled phase tailoring and stability of β-W for spintronic applications

Understanding the nucleation and growth of tungsten (W) is technologically important in spin-to-charge interconversion for realizing energy-efficient spintronic devices. Here, we have systematically investigated the effect of Ar deposition pressure (PAr) on the nucleation and growth of W. The observed surface topography as a function of PAr reveals a microstructural transition from zone T to zone 1 in the structure zone model. The physical origin for the increasing roughness as a function of PAr correlates with the surface diffusion of adatoms and growth kinetics in the Volmer–Weber growth mechanism. Grazing incidence x-ray diffraction (GIXRD) results show that W exhibits a structural phase transition from a mixed phase of (α+β)-W to a single phase of β-W as a function of PAr. The analysis of the electron diffraction patterns obtained from the films grown on amorphous-SiNx windows also supports these observations. The observed transition is fundamentally correlated with the growth kinetics in zone T and zone I. Thickness-dependent GIXRD results qualitatively prove that the film grown in zone T exhibits compressive strain, whereas that grown in zone I exhibits only tensile strain. The critical thickness for the phase transition is strongly attributed to the strain during nucleation and growth. The increasing resistivity as a function of PAr corroborates the change in structural phases. Thickness-dependent resistivity measurements correlate with the degree of crystallinity via relative intensity observed from the GIXRD results. Our results strongly suggest that W structural phases can be deterministically controlled via PAr for developing low-power spintronic devices.

Exploring the performance of Co/Al2O3–ZrO2 nanocatalysts developed through the thermal evaporation method in dry reforming of methane

Abstract This study aimed to investigate the performance of the thin layer nanostructures of Co/Al2O3–ZrO2 in the dry reforming of methane (DRM) in a microchannel reactor. The nanostructures were prepared via utilizing the thermal evaporation method. Reactor tests were carried out at various coating times of 2, 3, and 4 min and temperatures of 700, 750, and 800 °C with a feed flow rate of 10 ml/min and a 1:1:8 ratio of helium, carbon dioxide, and methane. Also, grazing incidence X-ray diffraction (GIXRD), field emission scanning electron microscopy (FESEM), and energy-dispersive X-ray (EDX) were used to identify catalyst features. According to the obtained results, the highest percentage of conversion in all samples was observed at 800 °C. The results of the reactor tests also revealed that the activity of catalyst layers highly depends on coating time. The findings demonstrated that raising deposition time improves the distribution of particle size and catalyst loading. Considering the nanostructure of Co/Al2O3–ZrO2, the sample undergoing 4 min coating time yielded the highest amount of primary methane conversion (89.3 %), primary carbon dioxide conversion (92.4 %), and H2/CO molar ratio (0.91). The stability test of the catalyst layers for 28 h at the optimum condition (P = 1 atm, T = 800 °C, t = 4 min deposition time, CH4/CO2 = 1, and GHSV = 48,000 mL g−1 h−1) showed that the catalysts prepared by this method had a good stability.

The effect of RF sputtering power on structural, nanomechanical and tribological properties of single layered TaN coatings

Single-layered TaN thin coatings were deposited on Ti6Al7Nb alloy substrates using reactive radiofrequency magnetron sputtering, with variations in target power. To assess the crystalline structure, chemical composition, and surface topography of these coatings, Grazing Incidence x-ray Diffraction (GIXRD), Energy Dispersive Spectroscopy (EDS), and Scanning Probe Microscopy (SPM) were employed, respectively. The study revealed that deposition power impacts the structure and composition of TaN coatings. Further analysis using x-ray Photoelectron Spectroscopy (XPS) indicated that the TaN coatings predominantly consisted of Ta and N, with trace amounts of oxygen (O 1s). Additionally, nanomechanical testing was conducted to evaluate hardness (H), modulus (E), and scratch properties. Results suggested that multiphase hex-TaN coatings exhibited superior H, E, and scratch properties compared to other cubic-structured TaN coatings. Friction and wear properties against steel balls under dry sliding conditions were determined using a ball-on-disk nanotribometer. The findings showed that mix-phase TaN coating exhibited a minimum coefficient of friction of 0.054 and a wear rate of 2.14 × 10−6 mm3/N.m. Abrasion, ploughing and oxidation were identified as the primary wear mechanism responsible for the wear of the TaN coatings.

Effect of Temperature on the Structure and Tribological Properties of Ti, TiN and Ti/TiN Coatings Deposited by Cathodic Arc PVD

Monolayers of Ti and TiN coatings, as well as a Ti/TiN bilayer coating, were deposited on AISI M2 steel substrates using the PVD cathodic arc technique. The coatings had a thickness close to 5 μm and an average roughness between 98.6 and 110.1 μm due to the presence of microdroplets on the surface. The crystalline structure of the materials was analyzed using Grazing Incidence X-ray Diffraction (GIXRD) with an increase in temperature to study the dynamics of oxide formation. A phase composition study was conducted using the Rietveld refinement method. At the temperatures where critical growth of titanium oxides, both anatase and rutile, was observed, pin-on-disk tests were performed to study the tribological properties of the materials at high temperatures. It was determined that the oxidation temperature of Ti is around 450 °C, promoting the formation of a combination of anatase and rutile. However, the formation of rutile inhibits the formation of anatase, which is stable above 600 °C. In contrast, TiN showed an oxidation temperature of 550 °C, with an exclusive growth of the rutile phase. The Ti/TiN bilayer exhibited mixed behavior, with the initial growth of anatase promoted by Ti, followed by the formation of rutile. Oxidation and tribo-oxidation dominated the wear behavior of the surfaces, showing a transition from mechanisms related to abrasion at low and medium temperatures to a combination of abrasion and adhesion mechanisms at high temperatures (800 °C).

Internal strain identification of seed-layered ZrO2, aluminum-, and yttrium-doped ZrO2 thin films via grazing incidence x-ray diffraction

Grazing incidence x-ray diffraction reveals that conventional post-deposition-annealed ZrO2 and in situ crystallized (by local epitaxy) ZrO2 thin films (<15 nm) have different internal strain states. A comparison between single- and two-step grown films enables the diverse strain components to be discretely identified. In particular, thickness-dependent intrinsic growth strain is unevenly distributed within the film according to the Volmer–Weber growth. Furthermore, extrinsic thermal strain, locally present in the annealed seed layer, does not spread over the in situ crystallized upper main layer of the two-step film. Post-deposition annealing of the two-step film renders the strain state identical to the single-step films by imposing thermal strain on the in situ crystallized main layer. Local strains created by diffused aluminum and yttrium dopants are also examined. Since each stress factor plays a vital role in the phase formation and electrical behaviors of ZrO2 and other fluorite-structure films, this method will pave the way for understanding the film's internal strain distribution and accompanying performance engineering.

Binder-free nickel/boron-doped diamond film electrodes for hydrogen evolution reaction in alkaline medium: Effect of nickel catalyst nanostructure on electrochemical performance

Boron-doped diamond (BDD) is a robust electrode material, and Ni metal is a promising alternative electrocatalyst to noble metals for promoting the hydrogen evolution reaction. In this study, binder-free Ni/BDD film electrodes, with Ni acting as a catalyst, were constructed. With thermal annealing temperature regulation, the Ni catalyst exhibited different nanostructures, including amorphous continuous films, partially crystalline corrugated films, and uniformly dispersive nanoparticles. The electrodes were characterized via scanning electron microscopy, grazing-incidence X-ray diffraction, and X-ray photoelectron spectroscopy. Furthermore, the impact of the Ni catalyst fine structure on the hydrogen evolution reaction performance was evaluated. The results highlighted the versatility of BDD as a platform for developing binder-free Ni/BDD electrodes. Through precise adjustment of the nano-scale structure of Ni catalysts on the BDD surface, high hydrogen evolution reaction activity was achieved, with an overpotential as low as 273 mV at 10 mA/cm2 in a 1 M KOH solution.

Comparative analysis of microstructural, compositional, and grazing incidence characteristics of oxide scale on 316L steel: SLM vs. wrought conditions

The aim of this research is to compare the oxidation behavior and characteristics of oxide scale of 316L steel produced by two methods: selective laser melting (SLM) and conventional casting and forming (wrought). To this end, the initial composition and microstructure of samples produced by those methods were first studied. Thermogravimetric analysis (TGA) and long-term isothermal oxidation tests were carried out on the samples and the oxidation kinetics were compared. The oxidized samples were then examined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and grazing incidence X-ray diffraction (GIXRD). The results indicated that in the temperature range of 600 °C–900 °C, the oxidation resistance of the SLM alloy is lower than that of the wrought alloy, especially at 800 °C. This is attributed to the combined effect of: i) smaller grain size due to the rapid solidification in the SLM alloy that increases the paths of oxygen penetration, ii) lower presence of chromium and manganese elements in the oxide layer and iii) preferential growth of iron oxide in the form of hillocks on the surface. Surface and cross-section analysis of the oxide layers show that iron oxide is dominant on the surface of the SLM sample at temperatures of 600 °C and 800 °C, and at 800 °C its extended hilly growth leads to significant spallation of the oxide scale and an exponential increase in the oxidation rate. However, at 900 °C, with the formation of a continuous oxide layer containing Fe2MnO4 and CrMnO4, the oxidation rate significantly decreases in both alloys.

Tuning infrared emissivity of GdCoO3 thin films through Fe doping: Fabrication and mechanism

Using polymer-assisted deposition technology, GdCo1-xFexO3 (0 ≤ x ≤ 0.5) porous films with high infrared emissivity at high temperatures were prepared on Si (100) substrates. The composition and calcination temperature of the precursor are determined by TG-DSC. The structure and composition of the films are investigated using Grazing Incidence X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and Raman spectroscopy. The surface morphology and elemental composition of the films were analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The average infrared emissivity of GdCo1-xFexO3 (0 ≤ x ≤ 0.5) films at different temperatures (100–500 °C) in the range of 8–14 μm has been tested by an infrared emissivity meter. The results show that the GdCoO3 film with Fe doping concentration of 10 % exhibits the highest infrared emissivity of 0.89 at 500 °C. Possible mechanisms for the high infrared emissivity of the films at high temperatures are discussed.

Synthesis and Modification of Boron Nitride nanotubes using ion implantation

In this work, Chemical Vapour Deposition (CVD) has been used to synthesize boron nitride (BN) nanostructures, particularly nanotubes, and selectively introduce defects into the lattice of the synthesized BN nanostructures through ion implantation. Scanning electron microscopy (SEM) images show clear evidence of BN nanostructures and BN nanotubes (BNNTs), with the latter appearing as long, thin structures with diameters ranging from ⁓30–80 nm. Raman analysis show an E2g mode of vibration assigned to hexagonal BN (h-BN) at 1366 cm−1 after ion implantation, with increased intensity. Grazing incidence X-ray diffraction (GIXRD) spectra revealed a prominent peak between 54 and 56°, corresponding to the (004) h-BN reflection, which was used to determine the average lattice parameter c⁓0.662 nm representing the stacking direction of the BN layers. The majority of the samples had broad peaks, indicative of a nanocrystalline material. The only exception was the sample grown at 1200 °C, which was found to have a Scherrer crystallite size >100 nm. In contrast, the rest of the samples had an average size of 3.5 nm. Notable observations in this study include a significant rise in the size of the Raman derived crystallite domains in the nanostructures synthesized at 1100 and 1200 °C after ion implantation with boron ions at fluence 5 × 1014 ions/cm2.

Chemical Bonding and Crystal Structure Schemes in Atomic/Molecular Layer Deposited Fe-Terephthalate Thin Films.

Advanced deposition routes are vital for the growth of functional metal-organic thin films. The gas-phase atomic/molecular layer deposition (ALD/MLD) technique provides solvent-free and uniform nanoscale thin films with unprecedented thickness control and allows straightforward device integration. Most excitingly, the ALD/MLD technique can enable the in situ growth of novel crystalline metal-organic materials. An exquisite example is iron-terephthalate (Fe-BDC), which is one of the most appealing metal-organic framework (MOF) type materials and thus widely studied in bulk form owing to its attractive potential in photocatalysis, biomedicine, and beyond. Resolving the chemistry and structural features of new thin film materials requires an extended selection of characterization and modeling techniques. Here we demonstrate how the unique features of the ALD/MLD grown in situ crystalline Fe-BDC thin films, different from the bulk Fe-BDC MOFs, can be resolved through techniques such as synchrotron grazing-incidence X-ray diffraction (GIXRD), Mössbauer spectroscopy, and resonant inelastic X-ray scattering (RIXS) and crystal structure predictions. The investigations of the Fe-BDC thin films, containing both trivalent and divalent iron, converge toward a novel crystalline Fe(III)-BDC monoclinic phase with space group C2/c and an amorphous Fe(II)-BDC phase. Finally, we demonstrate the excellent thermal stability of our Fe-BDC thin films.

Examination of measurement by hard X-ray grazing incidence diffraction patterns of isolated lattices for 3D 1-nm resolution

Examination of measurement by hard X-ray grazing incidence diffraction patterns of isolated lattices for 3D 1-nm resolution

Multi-scale wear mechanism of material surface and hinge interface based on TC4 alloy in space environment

PurposeThe purpose of this paper is to clarify the influence of low earth orbit space environment on the wear mechanism of TC4 alloy material and crank rocker mechanism.Design/methodology/approachIn this study, friction experiments were carried out on TC4 alloy friction discs and crank rocker mechanisms, both before and after exposure to atomic oxygen and proton irradiation. Nanoindentation, grazing incidence X-ray diffraction (GIXRD), and X-ray photoelectron spectroscopy were employed to systematically characterize alterations in mechanical properties, surface phase, and chemical composition.FindingsThe results show that the wear mechanism of TC4 alloy friction disc is mainly adhesive wear in vacuum environment, while the wear mechanism of crank rocker mechanism includes not only adhesive wear but also abrasive wear. Atomic oxygen exposure leads to the formation of more oxides on the surface of TC4 alloy, which form abrasive particles during the friction process. Proton irradiation will lead to a decrease in fatigue performance and an increase in hardness on the surface of TC4 alloy, thus causing fatigue wear on the surface of TC4 alloy, and more furrows appear on the crank rocker mechanism after proton irradiation. In the three environments, the characteristics of abrasive wear of the crank rocker mechanism are more obvious than those of the TC4 alloy friction disc.Originality/valueThese results highlight the importance of understanding the subtle effects of atomic oxygen and proton irradiation on the wear behavior of TC4 alloy and provide some insights for optimizing its performance in space applications.Peer reviewThe peer review history for this article is available at: https://publons.com/publon/10.1108/ILT-02-2024-0051/

Microstructural characterization of nanocrystalline hexagonal boron nitride thin films deposited by ion-beam assisted pulsed laser deposition

In recent years, hexagonal boron nitride (hBN) thin films have garnered considerable attention across various fields, including electronics, anti-corrosion coatings, tribology, and optoelectronics. Boron nitride films produced via physical vapor deposition typically result in amorphous microstructure and suffer from issues such as cracking and delamination. The synthesis of crystalline hBN thin films typically demands higher processing temperatures, toxic gas precursors, and catalytic metal substrates. Hence, this research aims to produce crystalline hBN films at relatively lower temperatures without toxic gas precursors. hBN thin films were deposited on silicon (100) substrates at 600 °C using an ion beam-assisted pulsed laser deposition. The study explores the microstructural evolution and surface morphology of deposited films under different Ar:N2 gas mixtures (ranging from 0% to 100% N2) and varying ion beam energies (from 0 to 400 eV). Microstructural analysis showed the hBN nanocrystallite formation in films deposited with N2 content of 50% and higher and an ion beam energy equal to or exceeding 200 eV, and the crystallite size was measured to be ∼24±8 nm. Raman spectra, grazing incidence X-ray diffraction, and transmission electron microscopy confirm the presence of hBN phase in as-deposited films. Films deposited with an N2 content of ≥50% and ion beam energy of ≥200 eV showed improved crystallinity, increased island size, and density of hBN nanocrystallites. The addition of ion bombardment comparatively made films rougher due to grain growth and formation of larger hBN nanoislands, and surface roughness increased with an increase in N2 content and ion beam energy. The results indicate that the ion beam bombardment facilitates nanograin formation and improves the crystallinity of hBN films even at lower deposition temperatures, offering the promise of advancing their use into practical applications across various fields.

Growth of high quality polycrystalline InGaO thin films by spray pyrolysis for coplanar thin-film transistors on polyimide substrate

The current mobile devices are moving towards flexible electronics. Introducing crystalline oxide semiconductors on flexible substrates is important to satisfy the requirements of high-resolution displays on flexible substrates. This study investigates the low-cost, as-grown polycrystalline (Poly) InGaO thin film transistor by spray pyrolysis on polyimide (PI) substrate. Grazing Incidence X-ray Diffraction (GI-XRD) measurements demonstrate that In0.8Ga0.2O, In0.7Ga0.3O, and In0.5Ga0.5O compositions exhibit crystallization on-set temperatures of ∼330, ∼350, and ∼415°C, respectively. Poly-In0.7Ga0.3O thin film with lower oxygen-vacancy (∼15 %) and less than 5 % O-H group could be achieved at the substrate temperature of 370°C. The hysteresis-free device performance with an average saturation mobility of 43.73 cm2V−1s−1 has been obtained using the poly-In0.7Ga0.3O with optimized N2O plasma treatment on the poly-oxide thin film. The TFTs show remarkable stability under humid environments and various stress conditions such as positive bias temperature, negative bias temperature, and mechanical stresses. In addition, the 96-stage gate shift register made of poly-In0.7Ga0.3O TFTs by spray pyrolysis exhibits the rising and falling times of less than 820 ns. Therefore, the poly-In0.7Ga0.3O TFTs by spray pyrolysis could be used for high-resolution, cost-effective, flexible active-matrix light-emitting displays.

Impact of the nature of the linker on the 2D and 3D organization of lipid-phenalenone conjugates

A series of phenalenone-lipid conjugates (1A, 1B, 1C, 2) have been synthesized to compensate for the poor water solubility of the photosensitizer phenalenone (PN) and promote the formation of nano-assemblies. We show that the organization and structure of monolayers upon compression strongly depend on the nature of the linker connecting PN to the lipid backbone, and the number of C18 chains. Monolayer properties at the air-water interface were analyzed by surface pressure measurements, Brewster angle and atomic force microscopies, grazing incidence X-ray diffraction, and X-ray reflectivity. Whereas conjugate 1C (ester bond) organizes into multilayers upon compression, conjugates 1A, 1B, and 2 form stable monolayers whose structure is controlled by van der Waals (vdW) interactions between C18 chains, intermolecular H-bonding involving the linker, and for 1B, π-π stacking of PN moieties. Conjugate 1A (amide-triazole linker) is structured into a rectangular network of chains with an order that extends only to the molecule of the adjacent cell. Conjugate 1B (amide bond) forms two incommensurate networks, one for the chains and the other for the headgroups. The distance between molecules in the next near neighbor chain lattice and the sufficient degree of freedom of PN groups allow the latter to pile up via π-π interactions below the chains in a rectangular cell. Conjugate 2 with its double chain adopts a similar behavior to that of a saturated phospholipid. Strong vdW interactions predominate and allow, at high surface pressure, hexagonal packing with no chain tilt. The distance between molecules prevents PN stacking. The identified PN derivative structures explain the linker’s impact on the formation and stability of nano-assemblies.

The laser pump X-ray probe system at LISA P08 PETRA III.

Understanding and controlling the structure and function of liquid interfaces is a constant challenge in biology, nanoscience and nanotechnology, with applications ranging from molecular electronics to controlled drug release. X-ray reflectivity and grazing incidence diffraction provide invaluable probes for studying the atomic scale structure at liquid-air interfaces. The new time-resolved laser system at the LISA liquid diffractometer situated at beamline P08 at the PETRA III synchrotron radiation source in Hamburg provides a laser pump with X-ray probe. The femtosecond laser combined with the LISA diffractometer allows unique opportunities to investigate photo-induced structural changes at liquid interfaces on the pico- and nanosecond time scales with pump-probe techniques. A time resolution of 38 ps has been achieved and verified with Bi. First experiments include laser-induced effects on salt solutions and liquid mercury surfaces with static and varied time scales measurements showing the proof of concept for investigations at liquid surfaces.

Crystalline as-deposited TiO 2 anatase thin films grown from TDMAT and water using thermal atomic layer deposition with in situ layer-by-layer air annealing

We report a new thermal atomic layer deposition (thermal-ALD) process including an air exposure as a third precursor to deposit crystalline TiO2 anatase thin films from tetrakis(dimethylamido)titanium(IV) (TDMAT) and water at deposition temperatures as low as 180 °C and film thicknesses as low as 10 nm. This ALD process enables TiO2-antase crystal growth during the deposition at low temperatures (< 220 °C). This additional oxidant pulse is used to fully oxidize the Ti to a 4+ state in the amorphous film, lowering the barrier to crystalline anatase formation. This new approach is informed by preliminary studies of post-deposition annealing (PDA) of thermal ALD films in both nitrogen and air atmospheres, which demonstrate the importance of having an oxidizing atmosphere to achieve the nucleation of the crystalline anatase phase. This oxidizing atmosphere is subsequently introduced into the ALD cycle as a third precursor and is shown to be more effective and efficient in promoting the crystalline transformation than even by post-deposition annealing. The crystalline anatase phase is verified by Raman spectroscopy and grazing incidence X-ray diffraction (GIXRD). The mechanism for crystallization during the TDMAT/H2O/air ALD cycle is probed by chemical state analysis via X-ray photoelectron spectroscopy (XPS). We propose that sub-oxidation in TiO2 thin films deposited by the thermal-ALD process inhibits crystallization during ALD from TDMAT/H2O chemistry. Scanning electron microscopy (SEM) is used to investigate the microstructure of these TiO2 thin films as a function of thickness (5 nm to 50 nm) and deposition temperature (180 °C to 220 °C). The reported layer-by-layer air anneal process is found to crystallize entire films in shorter total process times than thermal-ALD with ex situ post deposition annealing at identical temperatures, presumably due to the improved surface diffusion kinetics accessed during the deposition process.